CN101418383B - Method for preparing TiCl4 from titanium-containing furnace slag - Google Patents
Method for preparing TiCl4 from titanium-containing furnace slag Download PDFInfo
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- CN101418383B CN101418383B CN2008101805549A CN200810180554A CN101418383B CN 101418383 B CN101418383 B CN 101418383B CN 2008101805549 A CN2008101805549 A CN 2008101805549A CN 200810180554 A CN200810180554 A CN 200810180554A CN 101418383 B CN101418383 B CN 101418383B
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Abstract
The invention discloses a method for preparing TiCl4 through titanium-contained slag. The TiO2 content in the slag is 30 to 45 percent. The method is characterized in that the titanium-contained slag is directly reduced at a high temperature; and the reduced slag is used to prepare the TiCl4 through low-temperature boiling chlorination. According to the method, the titanium-contained slag, a reducer and a binding agent are mixed evenly and are used to make pellets; the pellets are reduced at the high temperature; the reduced pellets are crushed after being cooled down; and then the TiCl4 is obtained through the low-temperature boiling chlorination. The method has the advantages of low reducing temperature, short technical process, high total titanium recovery rate, and the like.
Description
Technical field
The present invention relates to metallurgy and chemical technology field, relate in particular to a kind of TiO
2Content is that 30%～45% Ti-containing slag prepares intermediates TiCl
4Method.
Background technology
The Ti-containing slag of discharging is a kind of abundant titanium resource in the smelting of titanium products is produced.Ti in the Ti-containing slag is with TiO
2Form compose and to be stored in each mineral, remove TiO
2Also contain very high MgO, CaO, SiO outward,
2Deng impurity,, will cause the wherein a large amount of losses and the waste of titanium resource if directly handle as waste residue.Therefore, Ti-containing slag is recycled through technical finesse, both can be obtained good economic benefits, and improve environment again, its social benefit highly significant.
Have at present and adopt sulfuric acid process to carry out the technology that titanium white is produced in acidleach, but too many, had a strong impact on performances such as the whiteness of made titanium white and reducing power because of foreign matter content in the slag.Produce TiCl if directly carry out chlorination
4, because of TiO
2The temperature of chlorination reaction is very high, even carburizing chlorination also will be more than 1100 ℃, impurity such as MgO, CaO can chlorination reaction take place earlier and generate low-melting MgCl
2, CaCl
2, these low melting points, high-boiling-point impurity meeting fusion, bond other compositions, caking influence fluidizing velocity, even destroy its fluidisation.
Chinese patent 87107488.5 discloses a kind of method from preparing titanic chloride using carbon-containing slag, its treatable TiO
2Content is 15%～35%.This method is to carry out earlier the high temperature cabonization reduction to handle in electric furnace, carries out low temperature chlorination again and prepares TiCl
4, its carbonization temperature up to 1600 ℃～1800 ℃, cause that most of material is in molten state in the slag, sharply increase because of the TiC that produces in the carbonization process can make the slag viscosity after the reduction again, therefore influence its quality of coming out of the stove.
Chinese patent 200410087636.0 also discloses and a kind ofly the titanium enrichment has been grown up be the method for TiN, but this patent need add the mineralizer and the complex technical process of growing up.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the above preparation titanium white technology, propose to use TiO
2Content is that the Ti-containing slag of 30%-45% is handled by high temperature reduction, carries out low-temperature boiling chlorating process again, makes the Ti in the Ti-containing slag finally be converted into TiCl
4The preparation method.
The present invention is achieved through the following technical solutions its purpose: adopt a kind of Ti-containing slag to prepare TiCl
4Method, its characteristics are Ti-containing slag is at high temperature directly reduced processing, chlorination prepares TiCl to the slag after the processing through low-temperature boiling
4, its processing step is as follows:
A is with TiO
2Content is that Ti-containing slag, reductive agent and the add-on of 30%-45% is that the binding agent of the 1%-6% of Ti-containing slag is crushed to below 80 orders, mixes then, and makes pellet; The add-on of reductive agent also should satisfy carbon content makes the titanium in the Ti-containing slag all be converted into titanium carbide, and FeO all be reduced into Fe the theoretical amount sum 110%～120%;
B finish mix ball at high temperature reduces processing, and the reduction treatment temp is 1200 ℃-1500 ℃, and the recovery time is 1-8 hour;
Pellet after the c reduction is handled carries out fragmentation after cooling, particle size after cracking is 0.074mm-0.25mm;
The compound slag of d after with fragmentation is to carry out the low-temperature boiling chlorination between 300 ℃-650 ℃ at chlorination temperature, obtains TiCl
4
Reductive agent described in the technical scheme can be the combination of one or more carbonaceous materials of graphite, hard coal, bituminous coal, coke; Described binding agent can be one or more mixing in wilkinite, polyvinyl alcohol, the water glass; In the high temperature reduction process, can add nitrogen and regulate atmosphere; The equipment of handling that reduces can be rotary kiln, tunnel furnace and shaft furnace.
The present invention passes through 1200 ℃-1500 ℃ high temperature reduction, makes the TiO in the Ti-containing slag
2Mainly be converted into titanium and carbon (nitrogen) change titanium at a low price after the reduction.Its chlorination temperature low (but 300 ℃-650 ℃ just chlorinations down), MgO, CaO are difficult for chlorination, can not destroy its fluidized state, so can reach good chlorination effect.Feed nitrogen in reduction process, not only can control reducing atmosphere, nitrogen can also participate in reaction, reduces reduction temperature, and reduction process is carried out under solid-state, and reduction process is easy to control.
The present invention has the following advantages: 1) reduction temperature is low, easily implements, and reduction back material still exists with solid form, can not be bonded on the reactor; 2) technical process is short, and its product is complied with the needs of market development for producing the raw material of titanium sponge and high-grade titanium dioxide; 3) influence of calcium in furnace magnesium to the chlorination operational stability evaded in chlorination at low temperatures after the titanium in the slag is handled through reduction; 4) the total yield height of titanium, the resource utilization height.
Embodiment
The TiO of Ti-containing slag of the present invention
2Content removes and contains TiO between 30%-45%
2Also contain very high MgO, CaO, SiO outward,
2, Al
3O
2, composition such as FeO.Adopt hard coal, coke powder, bituminous coal to carry out in resistance furnace, tunnel furnace, shaft furnace among the embodiment respectively, various reductive agent chemical ingredientss see Table 1, table 2, table 3, in the slag of reduction back the main tax situation of depositing of titanium see Table 4, shown in the table 5, table 6.
Embodiment 1:
Adopt TiO
2Content is that 38.31% Ti-containing slag is a raw material, and the about 3kg of Ti-containing slag, hard coal are reductive agent, and hard coal is 25% of Ti-containing slag with addition of amount.Ti-containing slag and hard coal are crushed to 80 orders～200 orders and are mixed to even, mix the back as binding agent with polyvinyl alcohol solution 170ml (water and polyvinyl alcohol 20:1 preparation) with 320ml water, the Ti-containing slag compound that mixes put into binding agent prepare pellet on the balling disc, the particle diameter 10～12mm of pellet.Prepared pellet is packed into after seasoning in the resistance furnace of Si-Mo rod, and feeding flow is the nitrogen of 2L/min, in 1350 ℃ of insulations 4 hours down.
Embodiment 2:
Adopt TiO
2Content is that 34.7% Ti-containing slag is a raw material, the about 50kg of Ti-containing slag, coke powder 11kg is a reductive agent, Ti-containing slag and coke powder be crushed to 80 orders～200 orders and be mixed to evenly, with water glass as binding agent, the water glass dosage is 5% of a Ti-containing slag, Ti-containing slag and coke powder, water glass are mixed in mill disc, and prepare pellet on ball press, institute's pressure ball is that the ellipsoid shape (is about 5cm, wide about 3cm, high about 2cm).Prepared pellet is packed into after seasoning in the plumbago crucible, and plumbago crucible is packed into carry out reduction nitridation in the tunnel furnace and handle, and feeding flow is the nitrogen of 18L/min, in 1500 ℃ of insulations 8 hours down.
Embodiment 3:
Adopt TiO
2Content is that 45% Ti-containing slag is a raw material, the about 85kg of Ti-containing slag, bituminous coal 30kg is as reductive agent, with wilkinite as binding agent, its add-on is 1.5% of a Ti-containing slag, Ti-containing slag and bituminous coal is crushed between 100～200 orders and with wilkinite is mixed to evenly, in balling disc, add water and make ball, the particle diameter 6～8mm of pellet.Prepared pellet adds in the shaft furnace, and pelletizing carries out drying at the shaft furnace top, and feeding flow in the shaft furnace bottom is the nitrogen of 21L/min, carries out reduction nitridation, 1200～1250 ℃ of reduction nitridation temperature, 6 hours recovery times in high-temperature zone, shaft furnace middle part.
Table 1 hard coal chemistry is formed %
| Composition | FCd | Vd | Ad | S |
| Content | 78.51 | 5.21 | 16.28 | 0.588 |
Table 2 coke powder chemical constitution %
| Composition | FCd | Vd | Ad | S |
| Content | 86.15 | 1.5 | 11.5 | — |
Table 3 bituminous coal chemical constitution %
| Composition | FCd | Vd | Ad | S |
| Content | 72.64 | 25 | 17 | 1.5 |
Table 4 reduced blast furnace chemical analysis results %
| Composition | TTi | TiN | Ti 2+、Ti 3+ | TiC |
| Content | 22.62 | 23.38 | 2.52 | 1.80 |
Table 5 reduced blast furnace chemical analysis results %
| Composition | TTi | TiN | Ti 2+、Ti 3+ | TiC |
| Content | 20.82 | 25.64 | 0.968 | <0.5 |
Table 6 reduced blast furnace chemical analysis results %
| Composition | TTi | TiN | Ti 2+、Ti 3+ | TiC |
| Content | 26.61 | 28.5 | 4.36 | 0.10 |
The main chemical constitution % of table 7 chloride residue
| Composition | TTi | TFe | CaO | MgO | siO 2 | Al 2O 3 |
| Content | 2.16 | 2.80 | 4.71 | 25.47 | 23.53 | 19.44 |
From table 4,5,6 as can be seen, Ti-containing slag is through TiO behind the reduction nitridation
2All change into (carbon) titanium nitride and at a low price the form of titanium exist, its carbon nitriding rate all reaches more than 80%, titanium is converted at a low price that the transformation efficiency of titanium and (carbon) titanium nitride reaches 95%, and titanium and titanium carbonitride all can carry out chlorination reaction at low temperatures and prepare TiCl at a low price
4, through having improved the utilization ratio of titanium in the Ti-containing slag greatly after the reduction nitridation processing.
With embodiment 1 gained carbon nitrogenize slag crushing and screening, control size is carried out fluidizing chlorination on the fluidized-bed of Ф 50mm between 0.074～0.25mm, chlorination temperature is controlled between 300～650 ℃, chlorination process is rapid, collects in continuous charging, continuous discharging slag process and obtains thick TiCl
4,, obtain smart TiCl through exquisite removal of impurities
4, can be used as and produce various high-quality titanium white products.
The carbon nitrogenize slag of embodiment 2 and 3 gained is crushed between 0.074～0.25mm, on the fluidized-bed of Ф 200mm, carries out fluidizing chlorination.Chlorination temperature is controlled between 300～650 ℃, and chlorination process is rapid, does not have caking in the chlorination furnace, continuous charging, and continuous discharging slag is collected and is obtained thick TiCl
4,, just can make the smart TiCl that is fit to titanium sponge and chloride process titanium dioxide production through exquisite removal of impurities
4
The main chemical constitution of residue sees Table 7 after the chlorination, can find out that from table 7 the Ti-containing slag chlorination rate behind the process carbon nitriding treatment reaches 90%, the rate of recovery of the total titanium of Ti-containing slag reaches 85%, its residue main component is the oxide compound of calcium, magnesium, aluminium, can be used as the raw material or the admixture that prepare cement, materials for wall etc., improved the comprehensive utilization ratio of Ti-containing slag resource greatly.
Claims (5)
1. a Ti-containing slag prepares TiCl
4Method, it is characterized in that: Ti-containing slag is at high temperature directly reduced processing, and chlorination prepares TiCl to the slag after the processing through low-temperature boiling
4, its processing step is as follows:
A is with TiO
2Content is that Ti-containing slag, reductive agent and the binding agent of 30%-45% is crushed to below 80 orders, mixes, and makes pellet;
B finish mix ball at high temperature reduces processing, and the reduction treatment temp is 1200 ℃-1500 ℃, and the recovery time is 1-8 hour;
Pellet after the c reduction is handled carries out fragmentation after cooling, particle size after cracking is 0.074mm-0.25mm;
The compound slag of d after with fragmentation carries out the low-temperature boiling chlorination and obtains TiCl
4, chlorination temperature is 300 ℃-650 ℃.
2. Ti-containing slag according to claim 1 prepares TiCl
4Method, it is characterized in that described reductive agent is the combination of one or more carbonaceous materials of graphite, hard coal, bituminous coal, coke, its add-on should satisfy carbon content makes the titanium in the Ti-containing slag all be converted into titanium carbide, and FeO all be reduced into Fe the theoretical amount sum 110%～120%.
3. Ti-containing slag according to claim 1 prepares TiCl
4Method, it is characterized in that described binding agent is that in wilkinite, polyvinyl alcohol, the water glass one or more mix, its add-on is the 1%-6% of Ti-containing slag.
4. Ti-containing slag according to claim 1 prepares TiCl
4Method, it is characterized in that in the high temperature reduction process adding nitrogen and regulate reducing atmosphere.
5. Ti-containing slag according to claim 1 prepares TiCl
4Method, the equipment of handling that it is characterized in that at high temperature reducing is rotary kiln, tunnel furnace and shaft furnace.
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| CN101418383B true CN101418383B (en) | 2010-09-29 |
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Cited By (1)
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| CN103011267A (en) * | 2012-12-14 | 2013-04-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Low-temperature boiling chloridizing process |
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| CN101337689B (en) * | 2008-08-26 | 2010-12-01 | 攀钢集团有限公司 | Method for producing titanium tetrachloride using low grade titan raw material |
| CN101665871B (en) * | 2009-10-14 | 2012-08-08 | 攀钢集团研究院有限公司 | Method for producing titanium carbide slag |
| CN102399994B (en) * | 2011-11-18 | 2013-11-06 | 攀钢集团研究院有限公司 | Titanium slag smelting method |
| CN102776364B (en) * | 2012-08-16 | 2013-10-23 | 中冶北方（大连）工程技术有限公司 | Process for recovering titanium and iron from titanomagnetite tailings |
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| CN110817877A (en) * | 2019-11-18 | 2020-02-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Technological process for preparing TiC crystal grain by reduction and carbonization of titanium-containing blast furnace slag |
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| CN115010170B (en) * | 2022-07-04 | 2023-09-22 | 重庆大学 | TiCl preparation by using titanium-containing blast furnace slag 4 Is a method of (2) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011267A (en) * | 2012-12-14 | 2013-04-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Low-temperature boiling chloridizing process |
| CN103011267B (en) * | 2012-12-14 | 2014-07-09 | 攀钢集团攀枝花钢铁研究院有限公司 | Low-temperature boiling chloridizing process |
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Owner name: PANZHIHUA IRON AND STEEL GROUP CO., LTD. PANZHIHUA Free format text: FORMER OWNER: PANZHIHUA IRON AND STEEL GROUP CO., LTD. PANZHIHUA IRON + STEEL INSTITUTE OF PANZHIHUA IRON + STEEL GROUP CO., LTD. |
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Effective date of registration: 20100419 Address after: 611731, Tianlong Road, Chengdu hi tech Zone (West Zone, Sichuan) 1 Applicant after: Pangang Group Institute Co., Ltd. Co-applicant after: Pangang Group Co., Ltd. Co-applicant after: Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. Co-applicant after: Panzhihua New Steel & Vanadium Co., Ltd. Address before: 611731, Tianlong Road, Chengdu hi tech Zone (West Zone, Sichuan) 1 Applicant before: Pangang Group Institute Co., Ltd. Co-applicant before: Panzhihua Iron and Steel (Group) Co., Ltd. Co-applicant before: Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. |
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