CN101665871B - Method for producing titanium carbide slag - Google Patents
Method for producing titanium carbide slag Download PDFInfo
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- CN101665871B CN101665871B CN2009101804339A CN200910180433A CN101665871B CN 101665871 B CN101665871 B CN 101665871B CN 2009101804339 A CN2009101804339 A CN 2009101804339A CN 200910180433 A CN200910180433 A CN 200910180433A CN 101665871 B CN101665871 B CN 101665871B
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- titaniferous ore
- titanium
- ore
- titaniferous
- slag
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- 239000002893 slag Substances 0.000 title claims abstract description 117
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 87
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003723 Smelting Methods 0.000 claims abstract description 40
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000008188 pellet Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000005453 pelletization Methods 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 5
- 239000011707 mineral Substances 0.000 abstract description 5
- 230000000630 rising effect Effects 0.000 abstract description 5
- 230000002159 abnormal effect Effects 0.000 abstract 1
- 238000005187 foaming Methods 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 abstract 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 abstract 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 16
- 238000005255 carburizing Methods 0.000 description 9
- 238000005660 chlorination reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 241001062472 Stokellia anisodon Species 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- KEHCHOCBAJSEKS-UHFFFAOYSA-N iron(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Fe+2] KEHCHOCBAJSEKS-UHFFFAOYSA-N 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for producing titanium carbide slag, comprising the steps of: heating raw material mixture containing first titanium-containing mineral, second titanium-containing mineral and pellets containing carbonaceous reducing agent and third titanium-containing mineral by a reactor; and leading the carbonaceous reducing agent to react with titanium oxides and iron oxides in the first, the second and the third titanium-containing minerals to respectively generate titanium carbide and simple substance of iron. The method can improve the carburization effect of a carbonaceous reducing molten pool in the high temperature carbonization process, thus easily controlling the finishing point of smelting; in addition, the method also reduces abnormal furnace conditions such as foaming slag, rising hearth, etc.
Description
Technical field
The present invention relates to the titanium field of metallurgy, particularly a kind of method of producing titanium carbide slag by titaniferous ore.
Background technology
Recycle about the titanium resource in the titaniferous ore, high temperature cabonization-low temperature chlorination is produced TiCl
4Technology and other operational path (like sulfuric acid to leach system titanium white and carry scandium, electrosmelting is produced titanium silicon etc.) compare and have that technical process is short, processing power is big, put forward the high advantage of titanium yield, and have good research basis and industrialization platform.High temperature cabonization-low temperature chlorination is produced TiCl
4Operational path substantially as follows: at high temperature to the TiO in the titanium-containing blast furnace slag
2Carry out carbonization, make titanium-containing blast furnace slag change into titanium carbide slag, utilize the characteristic of titanium carbide that it is carried out the low temperature selective chlorination again, make titanium carbide change into TiCl
4, and then be processed into refining TiCl
4, TiCl
4It is the raw material that chlorination is produced titanium white.
The process of titanium-containing blast furnace slag reduction and carbonization is TiO
2Gradual deoxidizing finally generates the process of titanium carbide.Because titanium-containing blast furnace slag TiO
2Content low (15%～30%), proportion is about 2.0g/cm
3～2.2g/cm
3, the less (0.8g/cm of carbonaceous reducing agent proportion
3～1.2g/cm
3), so titanium-containing blast furnace slag can't effectively mix with carbonaceous reducing agent in the carbonation reaction, makes the carburizing weak effect in high temperature cabonization process carbonaceous reduction molten bath to cause smelting endpoint uncontrollable.When smelting endpoint was uncontrollable, the time and the process of regulating terminal point prolonged, and cause melting electric consumption significantly to increase.
In addition; Titanium-containing blast furnace slag is typical short slag; Fusing point is high, and is mobile poor, simultaneously since the dystectic titanium carbide that generates in the smelting process be disperse state be distributed in inside, molten bath and along with smelting process constantly to the furnace bottom enrichment; Cause the unusual working of a furnace such as foamy slag and furnace bottom rising, have a strong impact on simultaneously and slag tap.Chinese patent CN101168801A discloses a kind of method of control foamed slag of titaniferous materials reduction and carbonization process; But adopt this method to be unfavorable for bringing into play furnace power; 50% of the common not enough rated output of electrosmelting intensity is unfavorable for energy-saving and cost-reducing and large-scale production.
Summary of the invention
One object of the present invention is to provide a kind of method of producing titanium carbide slag, and this method can be improved the carburizing effect in carbonaceous reduction molten bath in the high temperature cabonization process, thereby can easily control smelting endpoint.
Another object of the present invention is to provide a kind of method of producing titanium carbide slag, this method can reduce the unusual working of a furnace such as foamy slag and furnace bottom rising.
Method according to production titanium carbide slag of the present invention may further comprise the steps: contain first titaniferous ore, second titaniferous ore and comprise carbonaceous reducing agent and the raw mix of the pelletizing of the 3rd titaniferous ore with the reactor drum heating, make titanium oxide and ferriferous oxide reaction in the carbonaceous reducing agent and first titaniferous ore, second titaniferous ore, the 3rd titaniferous ore generate titanium carbide and iron simple substance respectively.
According to an aspect of the present invention, first titaniferous ore is the slag of smelting vanadium-titanium magnetite by blast furnace by-product, the TiO of first titaniferous ore
2Mass content is 15%～28%, and all iron content is 3%～10%.
According to an aspect of the present invention, all iron content of second titaniferous ore is 5%～35%, and all iron content of the 3rd titaniferous ore is 5%～35%.
According to an aspect of the present invention, the TiO of second titaniferous ore
2Mass content is 10%～40%, the TiO of the 3rd titaniferous ore
2Mass content is 10%～40%.
According to an aspect of the present invention; Second titaniferous ore is low-grade titanium ore, the titanium slag collected ash smelting dust-removal system and capture, with at least a in the titanium slag that molten branch is produced of the metallized pellet of rotary hearth furnace reduction vanadium titano-magnetite gained, the 3rd titaniferous ore is low-grade titanium ore, the titanium slag collected ash smelting dust-removal system and capture, with at least a in the titanium slag that melts branch production of the metallized pellet of rotary hearth furnace reduction vanadium titano-magnetite gained.
According to an aspect of the present invention, carbonaceous reducing agent comprises at least a in coke, hard coal, refinery coke, the steel-smelting and carburating agent.
According to an aspect of the present invention, the water cut of pelletizing is not more than 5%, and the dry bulb tap density is not less than 1.5g/cm
3
According to an aspect of the present invention, carbonaceous reducing agent the 20%～50%, the 3rd titaniferous ore that accounts for carbonaceous reducing agent and the 3rd titaniferous ore total amount accounts for carbonaceous reducing agent and the 3rd titaniferous ore total amount 50%～80%.
According to an aspect of the present invention; Reactor drum is an electric furnace, and it is 900 ℃～1450 ℃ first titaniferous ore electric furnace of packing into that this method is included in before the heating raw mixture second titaniferous ore and temperature, makes the material intensification of adding afterwards; When being warming up to 1650 ℃～1700 ℃; To the part of electric furnace adding pelletizing, under 1450 ℃～1750 ℃, carry out carbonization, in the process of carbonization, add remaining pelletizing.
According to an aspect of the present invention; Reactor drum is an electric furnace, and it is 900 ℃～1450 ℃ first titaniferous ore electric furnace of packing into that this method is included in before the heating raw mixture second titaniferous ore and temperature, makes the material intensification of adding afterwards; In the process that is warming up to the preset temperature in 1650 ℃～1700 ℃; To the part of electric furnace adding pelletizing, under 1450 ℃～1750 ℃, carry out carbonization, in the process of carbonization, add remaining pelletizing.
According to an aspect of the present invention; With second titaniferous ore and temperature is that pack into the step of electric furnace of 900 ℃～1450 ℃ first titaniferous ore comprises: at first second titaniferous ore with cold conditions adds electric furnace, is 900 ℃～1450 ℃ first titaniferous ore electric furnace of packing into temperature then.
According to an aspect of the present invention, the TiO of second titaniferous ore
2Mass content is 10%～40%, the TiO of the 3rd titaniferous ore
2Mass content is 10%～40%; First titaniferous ore accounts for 50%～70%, second titaniferous ore of first titaniferous ore, second titaniferous ore and the 3rd titaniferous ore total amount and the total amount of the 3rd titaniferous ore accounts for 30%～50% of first titaniferous ore, second titaniferous ore and the 3rd titaniferous ore total amount.
According to an aspect of the present invention, the TiO of second titaniferous ore and the 3rd titaniferous ore
2Mass content is identical, and 50%～80%, second titaniferous ore that the 3rd titaniferous ore accounts for second titaniferous ore and the 3rd titaniferous ore total amount accounts for 20%～50% of second titaniferous ore and the 3rd titaniferous ore total amount.
According to an aspect of the present invention, the amount of carbon is that titanium oxide reaction in carbon and first titaniferous ore, second titaniferous ore, the 3rd titaniferous ore generates theory consumption carbon amount and the carbon of TiC and CO and consumes 135%～150% of carbon amount sum with the theory that ferriferous oxide reaction in first titaniferous ore, second titaniferous ore, the 3rd titaniferous ore generates Fe simple substance and CO in the carbonaceous reducing agent.
Embodiment
Describe working method below in detail according to titanium carbide slag of the present invention.
Working method according to titanium carbide slag of the present invention comprises: the raw mix that contains first titaniferous ore, second titaniferous ore and pelletizing with the reactor drum heating; This pelletizing comprises carbonaceous reducing agent and the 3rd titaniferous ore, makes titanium oxide and ferriferous oxide reaction in carbonaceous reducing agent and first titaniferous ore, second titaniferous ore, the 3rd titaniferous ore generate titanium carbide and iron simple substance respectively through heating.Term used herein " first ", " second " and " the 3rd " only are to be used for various titaniferous ores are made a distinction, and are not intended to limit the character of titaniferous ore, more are not intended to limit the scope of the invention.
First titaniferous ore can be the slag (being also referred to as titanium-containing blast furnace slag) of smelting vanadium-titanium magnetite by blast furnace by-product, and its chemical constitution is as shown in table 1.
Table 1
| Composition | TiO 2 | Al 2O 3 | MgO | CaO | TFe (full iron) |
| Content (wt%) | 15～28 | 10～16 | 5～8 | 20～30 | 3～10 |
| Composition | SiO 2 | V 2O 5 | C | MnO | Other |
| Content (wt%) | 17～19 | 0.2～0.25 | 0.4～5.2 | 0.3～0.5 | 1～3 |
Yet titanium-containing blast furnace slag used in the present invention is not limited to the slag behind the smelting vanadium-titanium magnetite by blast furnace, for example can be the slag behind the blast-furnace smelting ilmenite.And, the TiO in the titanium-containing blast furnace slag
2Content is not limited to 15%～28%, and TFe content is not limited to 3%～10%, can use TiO
2The titanium-containing blast furnace slag that content is higher or lower, TFe content is higher or lower.The content of mentioning in this specification sheets is mass percentage content.
Second titaniferous ore and the 3rd titaniferous ore comprise collected ash that low-grade titanium ore, titanium slag smelt dust-removal system and capture, with the metallized pellet of rotary hearth furnace reduction vanadium titano-magnetite gained titanium slag or its mixture through molten branch production.The TFe content of second titaniferous ore can be 5%～35%, TiO
2Content can be 10%～40%; The TFe content of the 3rd titaniferous ore can be 5%～35%, TiO
2Content can be 10%～40%.Second titaniferous ore can be identical or different with the 3rd titaniferous ore.
Low-grade titanium ore is often referred to that marketable value is low, the iron titanium oxide total amount is less than 80% titanium ore, comprises primary titanium ore, selects titanium mine tailing etc.The TFe content of low-grade titanium ore can be 15%～30%, TiO
2Content can be 10%～35%.The TFe content that titanium slag is smelted the collected ash of dust-removal system capture can be 20%～30%, TiO
2Content can be 10%～35%.Metallized pellet with rotary hearth furnace reduction vanadium titano-magnetite gained can be 5%～15% through the TFe content of the titanium slag of molten branch production, TiO
2Content can be 35%～40%.
The collected ash that low-grade titanium ore, titanium slag are smelted the dust-removal system capture is generally fine ore, and its granularity is generally accounting for more than 80% below 200 orders; Yet the granularity of above-mentioned mineral is not limited thereto, and can use littler fine ore of granularity or granularity bigger fine ore or lump ore.
Carbonaceous reducing agent comprises a kind of or its mixture in coke, hard coal, refinery coke, the steel-smelting and carburating agent.The granularity of carbonaceous reducing agent can be worked as with the granulometric facies of used the 3rd titaniferous ore of preparation pelletizing, for example can account for more than 80% below 200 orders; Yet the granularity of carbonaceous reducing agent is not limited thereto, and can use the littler or bigger carbonaceous reducing agent of granularity.
Can use the ball method of making commonly used to prepare the pelletizing that comprises carbonaceous reducing agent and the 3rd titaniferous ore.For example, can use balling disc or ball press to prepare wet bulb, adopt drying plant (for example electric furnace flue gas reducing apparatus) under 900 ℃～1250 ℃, wet bulb to be carried out drying then.Can make the water cut of dry back dry bulb be not more than 5%, the dry bulb tap density is not less than 1.5g/cm
3, can effectively avoid the explosivity of pelletizing in follow-up electrosmelting process to pulverize like this.
Carbonaceous reducing agent can account for 20%～50% of carbonaceous reducing agent and the 3rd titaniferous ore total amount; The 3rd titaniferous ore can account for 50%～80% of carbonaceous reducing agent and the 3rd titaniferous ore total amount; Select the purpose of these scopes to be mainly to guarantee that pellet density reaches value, promptly usually at 1.5g/cm
3More than.In addition, if the content of carbonaceous reducing agent and the 3rd titaniferous ore not in above-mentioned scope, then is difficult to ensure the carburizing effect of carbonaceous reducing agent in electric furnace.As well-known to those skilled in the art, be 100% based on the gross weight of carbonaceous reducing agent and the 3rd titaniferous ore, pelletizing can also add 1%～3% sticker, and sticker can be selected asphalt powder and bentonitic mixture for use.
According to the method for the invention, can adopt the reactor drum of electric furnace as carburizing reagent.
Second titaniferous ore that at first, can add cold conditions (for example under the normal temperature) to electric furnace through the reinforced feed bin on electric furnace body top.Then, can add temperature to electric furnace through slag car turndown device be 900 ℃～1450 ℃ hot titanium-containing blast furnace slag.Because the common granularity of second titaniferous ore is below 200 orders and be in cold conditions; If, then cause dust pollution easily and fly upward loss very big so in the smelting process in later stage or after adding hot titanium-containing blast furnace slag, add second titaniferous ore of cold conditions.In addition, add earlier cold conditions second titaniferous ore and can protect furnace bottom, prevent that hot titanium-containing blast furnace slag from going into infringement and the impact of stove process to bottom refractory.Therefore, preferably at first add cold conditions second titaniferous ore, add hot titanium-containing blast furnace slag again.
If the granularity of cold conditions second titaniferous ore is enough big; When perhaps adding cold conditions second titaniferous ore according to the production requirement needs; Can add cold conditions second titaniferous ore and hot titanium-containing blast furnace slag simultaneously, perhaps after hot titanium-containing blast furnace slag adds completion, add cold conditions second titaniferous ore.
In addition, under the situation of suitable hot second titaniferous ore of the charging temperature of use temperature and hot titanium-containing blast furnace slag, can be after adding hot titanium-containing blast furnace slag, add this hot second titaniferous ore before or simultaneously.
After coming out of the stove, the blast furnace slag that smelting vanadium-titanium magnetite by blast furnace produces directly to produce the raw material of the method for titanium carbide slag without cooling fully as the present invention; Yet, the invention is not restricted to this, can the titanium-containing blast furnace slag heating back of cold conditions be used as the raw material of method of the present invention.Temperature is higher than 1250 ℃ titanium-containing blast furnace slag and has good flowability; 900 ℃～1250 ℃ titanium-containing blast furnace slag is in the state between mobile disappearance (slag body crust or condense) and the good fluidity, can through tipple or change jar measure realize 900 ℃～1250 ℃ titanium-containing blast furnace slag go into stove.
Afterwards, the material of adding is heated up, when being warming up to 1650 ℃～1700 ℃, add the pelletizing that comprises carbonaceous reducing agent and the 3rd titaniferous ore, smelt to electric furnace.Reaction in the electric furnace comprises:
TiO
2+3C＝TiC+2CO
FeO+C＝Fe+CO
Fe
2O
3+3C＝2Fe+3CO。
When confirming the consumption of carbonaceous reducing agent, with reference to above-mentioned reaction, to the TiO in second titaniferous ore, titanium-containing blast furnace slag, the 3rd titaniferous ore
2, FeO, Fe
2O
3Carry out theory consumption carbon amount and calculate, the actual demand amount is 135%～150% of a theoretical consumption carbon amount, and then the add-on of definite pelletizing.
Usually titaniferous ore exists the TiC in the titanium carbide slag that technical requirements is arranged to tax after carbonization, and the recovery that promptly will guarantee to reclaim the Ti in the titaniferous ore is enough high.If the amount of the C in the carbonaceous reducing agent consumes 135% of carbon amount, then TiO less than theory
2The degree that is converted into TiC is not enough, i.e. TiO
2The recovery can not reach processing requirement.If the amount of the C in the carbonaceous reducing agent consumes 150% of carbon amount, then TiO greater than theory
2The degree that is converted into TiC improves, but transformation efficiency can reach more than the economic carbonation rate, thereby causes following problem: power consumption sharply increases, and is unfavorable to the economy of technology; Too much carbonaceous reducing agent certainly will cause scaling loss, finally increases the operating load of dust-removal system.In addition, too much carbonaceous reducing agent itself has improved the technology cost, and is unfavorable to the economy of technology.
Because need control reaction in furnace speed through the adding of carbonaceous reducing agent; The unusual working of a furnace such as control foam slag; So can when melt reaches reaction conditions (for example being suitable for taking place 1650 ℃～1700 ℃ of the temperature and the flowability that is suitable for taking place carburizing reagent of carburizing reagent), add the part (for example 50%～85%) of the pelletizing that comprises carbonaceous reducing agent and the 3rd titaniferous ore; In carbonization process, add the pelletizing that comprises carbonaceous reducing agent and the 3rd titaniferous ore then, to control reaction in furnace speed better in batches.In addition, can also after adding second titaniferous ore and first titaniferous ore, be warmed up to the pelletizing that adding in the process of preset temperature (certain temperature in for example 1650 ℃～1700 ℃) comprises carbonaceous reducing agent and the 3rd titaniferous ore.Under the hot situation of the raw material maintenance that adds electric furnace, add carbonaceous reducing agent; Can shorten the warm up time of reductive agent, prolong the time of whole carbonization, thus effective controls reaction speed; Control electric furnace system short-term flue gas generation can also suppress the generation of foamy slag to a certain extent.In addition, under the hot situation of the raw material maintenance that adds electric furnace, add carbonaceous reducing agent, reduced the scaling loss of reductive agent.
The consumption of titaniferous materials (i.e. first titaniferous ore, second titaniferous ore and the 3rd titaniferous ore) is confirmed according to the content of the titanium carbide in the titanium carbide slag finished product.
In addition, at the TiO of titanium-containing blast furnace slag
2Content is the TiO of 15%～28%, second titaniferous ore and the 3rd titaniferous ore
2Content is under 10%～40% the situation, and according to the processing requirement of existing titanium carbide slag low temperature chlorination, 50%～70%, second titaniferous ore and the 3rd titaniferous ore total amount that titanium-containing blast furnace slag accounts for the titaniferous materials total amount account for 30%～50% of titaniferous materials total amount.TiO at second titaniferous ore and the 3rd titaniferous ore
2Under the identical situation of content, 50%～80%, second titaniferous ore that the 3rd titaniferous ore accounts for second titaniferous ore and the 3rd titaniferous ore total amount accounts for 20%～50% of second titaniferous ore and the 3rd titaniferous ore total amount.Under the situation that at first adds second titaniferous ore, select the purpose of above-mentioned numerical range (50%～80%, 20%～50%) to be effectively to protect the electric furnace furnace bottom, effectively suppress furnace bottom rising.
Carburizing reagent is the gradual deoxidizing reaction, and its theoretical temperatures scope is 1200 ℃～1727 ℃, and the CaO in the too high then titanium-containing blast furnace slag of temperature, the reaction tendency of MgO are strengthened, and is commonly referred to the high-temperature selective carbonization so generate the carburizing reagent of titanium carbide.The smelting temperature of method of the present invention is controlled to be 1450 ℃～1750 ℃.Select 1450 ℃～1750 ℃ purpose to be that it partly is suitable for the scope of theoretical reaction temperature; In addition, suitably improve the temperature battery limit (BL), can improve smelting process slag superheating temperature, strengthen the dynamic conditions of reaction, promptly ventilation property and the flowability of melt in stove is better.
According to the method for production titanium carbide slag of the present invention, after the pelletizing that comprises carbonaceous reducing agent and the 3rd titaniferous ore is gone into stove, the TiO of carbonaceous reducing agent and the 3rd titaniferous ore
2The degree of reaction is carbonaceous reducing agent and TiO when adding carbonaceous reducing agent and titanium-containing blast furnace slag respectively
2Level of response compare greatly and to improve.In addition, it is bigger than the density of carbonaceous reducing agent self with the density of the pelletizing of the 3rd titaniferous ore to comprise carbonaceous reducing agent, and carbonaceous reducing agent is mixed with titanium-containing blast furnace slag with second titaniferous ore that adds separately effectively.Comprehensive above-mentioned two aspects can be improved the carburizing effect in carbonaceous reduction molten bath in the high temperature cabonization process according to the method for production titanium carbide slag of the present invention, thereby can easily control smelting endpoint.
When the electric furnace adding comprises the pelletizing of carbonaceous reducing agent and the 3rd titaniferous ore; Carbonaceous reducing agent at first is reduced into iron (more particularly with the 3rd titaniferous ore in the pelletizing, second titaniferous ore that adds separately and the ferriferous oxide in the titanium-containing blast furnace slag; At first the ferriferous oxide in the 3rd titaniferous ore is reduced into iron), the enrichment and be deposited on (or occupying) furnace bottom gradually of the molten iron of generation.Because the fusing point of molten iron is more much lower than titanium carbide, therefore furnace bottom can keep good mobility in smelting process.Therefore, can reduce the unusual working of a furnace such as foamy slag and furnace bottom rising, help slagging tap according to the method for production titanium carbide slag of the present invention.
Can adopt following two kinds of methods to confirm smelting endpoint.First method is under the situation of stable reinforced (technology conditions such as raw and auxiliary material and power consumption parameter are basicly stable, the operation direct motion), formulates carbide slag carbonation rate-tap to tap time (melting electric consumption) curve, and carbonation rate is as requested confirmed smelting endpoint.About second method, because composing with dark grey state in titanium carbide slag usually, deposits titanium carbide, so can judge smelting endpoint according to experience with reference to electrosmelting titanium slag smelting endpoint discrimination model.Adopt above-mentioned two kinds of methods to confirm that smelting endpoint is not very accurate usually; But under the situation of titanium carbide slag as the raw material of follow-up low temperature chlorination; The content requirement of titanium carbide is not very strict in the carbide slag, is controlled at the processing requirement that can satisfy follow-up low temperature chlorination between 10%～20% usually.
The Controllable Temperature of the titanium carbide slag when slagging tap is built in more than 1750 ℃, and fast slag tapping as far as possible.
The specific embodiment of the working method of titanium carbide slag of the present invention is described below.
Embodiment 1:
The raw material that the method for this embodiment is used is following: select 3.5 tons of titanium mine tailings (t), its TiO under the normal temperature
2Content is 32.50%, and TFe content is 29.1%, and granularity is to account for 80% below 200 orders (0.074mm); The hot titanium-containing blast furnace slag 15t of smelting vanadium-titanium magnetite by blast furnace by-product, its temperature is 1235 ℃, TiO
2Content is 20.75%, and FeO content is 2.5%, Fe
2O
3Content is 5.8%, and MFe (metallic iron) content is 2%; Comprise coke powder and the pelletizing that selects the titanium mine tailing; This pelletizing is prepared from through pressure ball, drying in 4.2t coke powder, above-mentioned titanium mine tailing, 175kg sticker, the water of selecting of 4.5t; Sticker is made up of 100kg wilkinite and 75kg asphalt powder; The fixed carbon content of coke powder is 78.0%, and the water cut of this pelletizing is 4%, and the dry bulb tap density is 1.55g/cm
3
Through belt conveyor the titanium mine tailing that selects under the above-mentioned normal temperature of 3.5t is added 9000kVA carbonization electric furnace furnace bottom, through slag car turndown device the above-mentioned hot titanium-containing blast furnace slag of 15t is added electric furnace then.Use crane transhipment body of heater to smelting the position, power input 8500kW～10000kW adds 75% of the total amount that comprises coke powder and the pelletizing that selects the titanium mine tailing when sending electricity to make material be warming up to 1650 ℃.Afterwards, add remaining coke powder and the pelletizing that selects the titanium mine tailing of comprising according to unusual working of a furnaces such as stove inner foam slags in batches.Begin from adding pelletizing for the first time, smelted 60 minutes, smelting temperature remains on 1650 ℃～1750 ℃.Slag tap, the titanium carbide content of measuring the finished product titanium carbide slag is 18.0%.
Embodiment 2:
The raw material that the method for this embodiment is used is following: the titanium slag electric furnace collected ash 4.0t under the normal temperature, its TiO
2Content is 25.5%, and TFe content is 27.1%, and granularity is to account for 90.5% below 200 orders (0.074mm); The hot titanium-containing blast furnace slag 18t of smelting vanadium-titanium magnetite by blast furnace by-product, its temperature is 1275 ℃, TiO
2Content is 21.45%, and FeO content is 2.4%, Fe
2O
3Content is 6.2%, and MFe content is 3%; The pelletizing that comprises hard coal and titanium slag electric furnace collected ash; This pelletizing is prepared from through pressure ball, drying in 4.5t hard coal, the above-mentioned titanium slag electric furnace collected ash of 6.5t, 200kg sticker, water; Sticker is made up of 155kg wilkinite and 45kg asphalt powder; Anthracitic fixed carbon content is 80.5%, and the water cut of this pelletizing is 3%, and the dry bulb tap density is 1.60g/cm
3
Through the manual work pack titanium slag electric furnace collected ash under the above-mentioned normal temperature of 4.0t is added 9000kVA carbonization electric furnace furnace bottom, through slag car turndown device the above-mentioned hot titanium-containing blast furnace slag of 18t is added electric furnace then.Use crane transhipment body of heater to smelting the position, power input 8500kW～10000kW send electricity to make material be warming up to 1700 ℃ with 65 minutes, in temperature-rise period evenly adding comprise hard coal and titanium slag electric furnace collected ash pelletizing total amount 74%.Be warming up to after 1700 ℃,, adding the remaining pelletizing that comprises hard coal and titanium slag electric furnace collected ash according to unusual working of a furnaces such as stove inner foam slags in the carbonization process in batches 1650 ℃～1750 ℃ following carbonizations 205 minutes.Slag tap, the titanium carbide content of measuring the finished product titanium carbide slag is 15.75%.
Embodiment 3:
The raw material that the method for this embodiment is used is following: the metallized pellet with rotary hearth furnace reduction vanadium titano-magnetite gained melts the hot titanium slag 5t that branch is produced through the molten stove that divides, and its temperature is 1550 ℃, TiO
2Content is 35%, and TFe content is 12.5%; The hot titanium-containing blast furnace slag 15t of smelting vanadium-titanium magnetite by blast furnace by-product, its temperature is 1425 ℃, TiO
2Content is 22.5%, and FeO content is 2.5%, Fe
2O
3Content is 5.3%, and MFe content is 2.0%; Comprise the steel-smelting and carburating agent with the metallized pellet of rotary hearth furnace reduction vanadium titano-magnetite gained through the molten pelletizing that divides the titanium slag of the molten branch production of stove; This pelletizing is prepared from through pressure ball, drying through cold conditions titanium slag, 220kg sticker, the water of molten branch production with the metallized pellet of rotary hearth furnace reduction vanadium titano-magnetite gained the agent of 5t steel-smelting and carburating, 7.5t; Sticker is made up of 165kg wilkinite and 55kg asphalt powder; The fixed carbon content of steel-smelting and carburating agent is 88.5%, the TiO of this cold conditions titanium slag
2Content is 35%, and TFe content is 12.5%, and granularity is to account for 75% below 200 orders (0.074mm), and the water cut of this pelletizing is 3.6%, and the dry bulb tap density is 1.78g/cm
3
Through the mobile slag car 9000kVA carbonization electric furnace is transported to the tap cinder mouth and accesses above-mentioned hot titanium-containing blast furnace slag 15t; Connect slag and accomplish the back and get into the molten minute stove side of slagging tap, change above-mentioned hot molten minute titanium slag of 5t over to 9000kVA carbonization electric furnace through ash shoot; Make electric furnace body directly return carbonization and smelt a position feeding temperature-raising, power input 8500kW～10000kW made material be warming up to 1750 ℃ with 60 minutes, in temperature-rise period, evenly added the above-mentioned pelletizing 10t that steel-smelting and carburating agent and cold conditions melt the branch titanium slag that comprises.Be warming up to after 1750 ℃,, adding remaining steel-smelting and carburating agent and the molten pelletizing that divides titanium slag of cold conditions of comprising according to unusual working of a furnaces such as stove inner foam slags in the carbonization process in batches 1650 ℃～1750 ℃ following carbonizations 210 minutes.Slag tap, the titanium carbide content of measuring the finished product titanium carbide slag is 19.85%.
Claims (5)
1. method of producing titanium carbide slag; It is characterized in that containing first titaniferous ore, second titaniferous ore and comprising carbonaceous reducing agent and the raw mix of the pelletizing of the 3rd titaniferous ore, make titanium oxide and ferriferous oxide reaction in the carbonaceous reducing agent and first titaniferous ore, second titaniferous ore, the 3rd titaniferous ore generate titanium carbide and iron simple substance respectively with the reactor drum heating; May further comprise the steps:
Before the heating raw mixture; At first second titaniferous ore of cold conditions being added electric furnace, is 900 ℃～1450 ℃ first titaniferous ore electric furnace of packing into temperature then, and the material of adding is heated up; When being warming up to 1650 ℃～1700 ℃; Add a said part that comprises the pelletizing of carbonaceous reducing agent and the 3rd titaniferous ore to electric furnace, under 1450 ℃～1750 ℃, carry out carbonization, in the process of carbonization, add remaining pelletizing;
Wherein, First titaniferous ore accounts for 50%～70%, second titaniferous ore of first titaniferous ore, second titaniferous ore and the 3rd titaniferous ore total amount and the total amount of the 3rd titaniferous ore accounts for 30%～50% of first titaniferous ore, second titaniferous ore and the 3rd titaniferous ore total amount;
The 20%～50%, the 3rd titaniferous ore that carbonaceous reducing agent accounts for carbonaceous reducing agent and the 3rd titaniferous ore total amount accounts for carbonaceous reducing agent and the 3rd titaniferous ore total amount 50%～80%, and the water cut of pelletizing is not more than 5%, and the dry bulb tap density is not less than 1.5g/cm
3
The TiO of first titaniferous ore
2Mass content is 15%～28%, and all iron content is 3%～10%; The TiO of second titaniferous ore
2Mass content is 10%～40%, and all iron content is 5%～35%; The TiO of the 3rd titaniferous ore
2Mass content is 10%～40%, and all iron content is 5%～35%.
2. the method for claim 1; It is characterized in that first titaniferous ore is the slag of smelting vanadium-titanium magnetite by blast furnace by-product; Second titaniferous ore is low-grade titanium ore, the titanium slag collected ash smelting dust-removal system and capture, with at least a in the titanium slag that molten branch is produced of the metallized pellet of rotary hearth furnace reduction vanadium titano-magnetite gained, the 3rd titaniferous ore is low-grade titanium ore, the titanium slag collected ash smelting dust-removal system and capture, with at least a in the titanium slag that melts branch production of the metallized pellet of rotary hearth furnace reduction vanadium titano-magnetite gained.
3. the method for claim 1 is characterized in that carbonaceous reducing agent comprises at least a in coke, hard coal, refinery coke, the steel-smelting and carburating agent.
4. the method for claim 1 is characterized in that the TiO of second titaniferous ore and the 3rd titaniferous ore
2Mass content is identical, and 50%～80%, second titaniferous ore that the 3rd titaniferous ore accounts for second titaniferous ore and the 3rd titaniferous ore total amount accounts for 20%～50% of second titaniferous ore and the 3rd titaniferous ore total amount.
5. the method for claim 1, the amount of carbon in the carbonaceous reducing agent of it is characterized in that are that the titanium oxide reaction in carbon and first titaniferous ore, second titaniferous ore, the 3rd titaniferous ore generates theory consumption carbon amount and the carbon of TiC and CO and consumes 135%～150% of carbon amount sum with the theory that ferriferous oxide reaction in first titaniferous ore, second titaniferous ore, the 3rd titaniferous ore generates Fe simple substance and CO.
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| CN109252052B (en) * | 2018-10-29 | 2020-02-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for judging blast furnace slag carbonization smelting end point |
| CN110156019A (en) * | 2019-06-21 | 2019-08-23 | 攀钢集团攀枝花钢铁研究院有限公司 | It is used to prepare the electric arc furnaces and titanium carbide slag preparation method of titanium carbide slag |
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