CN103570080B - A kind of method of titanium tetrachloride settling mud synthetical recovery iron trichloride - Google Patents
A kind of method of titanium tetrachloride settling mud synthetical recovery iron trichloride Download PDFInfo
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- CN103570080B CN103570080B CN201310551833.2A CN201310551833A CN103570080B CN 103570080 B CN103570080 B CN 103570080B CN 201310551833 A CN201310551833 A CN 201310551833A CN 103570080 B CN103570080 B CN 103570080B
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- titanium tetrachloride
- iron trichloride
- organic solvent
- mud
- ticl
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Abstract
The invention discloses a kind of method of titanium tetrachloride settling mud synthetical recovery iron trichloride, it is characterized in that, the method comprises the following steps: titanium tetrachloride settling mud first adopts heating vaporization or solvent leaching method Separation and Recovery TiCl wherein
4, then will be separated TiCl
4after the residue normal pressure that obtains or reduction vaporization reclaim iron trichloride wherein, or at separation TiCl
4after add organic solvent in the residue that obtains, filter after Selectively leaching iron trichloride wherein, filtrate is separated through normal pressure or underpressure distillation and obtains organic solvent and iron trichloride.It is simple that the present invention has technique, and production cost is low, and the iron trichloride purity obtained is high, advantages of environment protection.
Description
Technical field
The invention belongs to domain of inorganic chemistry, be specifically related to a kind of method of titanium tetrachloride settling mud synthetical recovery iron trichloride.
Background technology
Iron trichloride is a kind of conventional chemical reagent, and it is widely used in the industries such as chemical industry, metallurgy, building.Iron trichloride adopts chlorination process, scorification and solution synthetic method to prepare usually.Chlorination process is that in a vertical response reaction in furnace, the iron trichloride steam of generation and tail gas are discharged by the top of stove, enter trap condensation and obtain solid crystal-iron trichloride finished product with waste iron filing and chlorine for raw material.Scorification be at one with in the reactor of acid proof lining, make iron filings and dry chlorine gas react in the eutectic mixture (such as, 70%FeCl3 and 30%KCl) of iron protochloride and Repone K or sodium-chlor.The iron(ic) chloride distillation generated, and be collected in condensing chamber, obtain solid chlorine iron product.Solution synthetic method is dissolved in hydrochloric acid by iron filings, first generates iron protochloride, then pass into chlorine oxidation and become iron(ic) chloride.Iron trichloride strong solution through cooling, six water things of crystallization iron(ic) chloride.
Iron is ilmenite (FeTiO
3) in one of the chief elements, therefore for the production of in the rich titanium material of titanium tetrachloride more or less containing iron.Rich titanium material is at chlorination process, and iron is wherein chlorinated together with titanium, after chlorination furnace air cooling is solidifying, must contain FeCl
3thick TiCl
4liquid.FeCl
3at thick TiCl
4the so-called titanium tetrachloride settling mud of formation can be separated out by nature in liquid.Titanium tetrachloride settling mud is except FeCl
3, AlCl
3beyond solids, also carry a large amount of TiCl secretly
4, there is very high recovery value.But because titanium tetrachloride settling mud character is special, current part factory adopts the mode process precipitation mud returning chlorination furnace, TiCl wherein
4volatilization enters chlorination furnace gas and is recycled, and FeCl
3then major part enters chlorinated furnace slag or dust-slag collection is abandoned.But most factory is then lower due to its rich titanium item position used, and after mud returns chlorination furnace, furnace heat cannot balance, and has to titanium tetrachloride settling mud directly to be discarded.This is contaminate environment not only, also result in the waste of resource simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of method of titanium tetrachloride settling mud synthetical recovery iron trichloride.The method not only can TiCl in efficient recovery titanium tetrachloride settling mud
4, and can synthetical recovery FeCl wherein
3, thus improve resource utilization, decreasing pollution, protection of the environment.
Technical scheme of the present invention is:
A method for titanium tetrachloride settling mud synthetical recovery iron trichloride, comprises the steps:
The first step: remove closing containing aluminium chlorination in titanium tetrachloride settling mud
In crude titanic chloride precipitation mud, add the solid aluminium of ferric oxide, make the aluminium chlorine compound that contains wherein change into aluminum oxide, obtain solid aluminium titanium tetrachloride settling mud;
Second step: Separation and Recovery TiCl
4
Solid aluminium titanium tetrachloride settling mud is completely cut off air heating evaporation TiCl wherein
4, collection steam, condensation obtain titanium tetrachloride, and evaporation residue is for subsequent use; Or
Organic solvent (1) leaching TiCl wherein will added except aluminium titanium tetrachloride settling mud
4, filter containing TiCl
4solution and leach residue, containing TiCl
4solution again through distilling to obtain organic solvent (1) and TiCl
4;
3rd step: comprehensively recovering Fe Cl
3
The evaporation residue that second step is obtained or leach residue heating evaporation FeCl wherein
3, produce iron trichloride; Or
Organic solvent (2) is added, Selectively leaching FeCl wherein in the evaporation residue obtained at second step or leach residue
3, filter containing FeCl
3filtrate, containing FeCl
3filtrate again through distilling to obtain organic solvent (2) and iron trichloride.
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, in the first step, the ferric oxide added is that granularity is less than 60 object Fe
2o
3powder, Fe
2o
3addition by precipitation mud in AlCl
3all Al is transformed into AlOCl
2o
3the 0.5-5 amount doubly of chemical reaction stoichiometric number adds.
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, in second step, isolated air heating evaporation carries out under normal pressure or reduced pressure, and atmospheric evaporation temperature is 136-280 DEG C; Reduction vaporization temperature is 80-136 DEG C, and environmental stress is 0.09-0.1MPa.
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, in second step, described leaching is 1:0.25 ~ 25ml/ml by volume, crude titanic chloride is precipitated mud and organic solvent (1) stirring and evenly mixing, makes the TiCl carried secretly in mud
4enter organic solvent (1).
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, in second step, organic solvent (1) refer to containing 1 ~ 10 carbon atom, boiling point lower than 136 DEG C, be one or more in the hydrocarbon polymer of liquid or its chlorinated derivatives under normal temperature.
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, organic solvent (1) is selected from least one in monochloro methane, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, a chlorobutane, Skellysolve A, iso-pentane, normal hexane, isohexane, hexanaphthene.
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, in second step, described to containing TiCl
4the distillation of solution is lower than at the temperature of 136 DEG C, and normal pressure or underpressure distillation, preferential evaporation organic solvent wherein (1), the organic solvent (1) that condensation obtains returns precipitation mud leaching TiCl
4operation recycles.
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, in the 3rd step, FeCl described in heating evaporation
3be carry out under the condition of normal pressure or decompression, allow FeCl in evaporation residue or leach residue
3volatilization, condensation obtains iron trichloride; Atmospheric evaporation temperature is 280-500 DEG C; Reduction vaporization temperature is 150-280 DEG C, and environmental stress is 0.09-0.1MPa.
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, in the 3rd step, described organic solvent (2) is selected from one or more in methyl alcohol, ethanol, acetone.
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, in the 3rd step, the FeCl described in Selectively leaching
3refer to by solid-to-liquid ratio 1:0.5 ~ 15g/ml, the evaporation residue obtained by second step or leach residue mix with organic solvent (2), and 0 ~ 80 DEG C is stirred 0.5 ~ 50h, Selectively leaching FeCl wherein
3, filter and obtain leached mud and contain FeCl
3filtrate.
The method of a kind of titanium tetrachloride settling mud synthetical recovery of the present invention iron trichloride, in the 3rd step, described contains FeCl
3filtrate evaporation is lower than at the temperature of 280 DEG C, and normal pressure or underpressure distillation, selectivity volatilization organic solvent wherein (2), the organic solvent (2) that condensation obtains returns FeCl
3leaching operation recycles.
The present invention has the following advantages and effect compared with existing technology:
FeCl in titanium tetrachloride settling mud
3tiCl
4waste in production process.Advantage of the present invention is with titanium tetrachloride settling mud as FeCl
3raw materials for production, by adding croci as solid aluminium agent, TiCl is wherein reclaimed in isolated air heating evaporation
4, or add organic solvent (1) leaching TiCl wherein
4after, then reclaim FeCl
3.Because Al is stronger to the avidity of O than Fe to the avidity of O, after croci adds, the AlCl in mud
3react with it with AlOCl and generate Al
2o
3and FeCl
3, and aluminum oxide not only little but also in organic solvent (1) and (2) the solvability of heating volatile is all very little, thus make aluminium be fixed on precipitation mud in.Gu aluminium titanium tetrachloride settling mud, by under the condition of normal pressure or decompression, controls its vaporization temperature, is first separated TiCl
4, then comprehensively recovering Fe Cl
3, valuable element is wherein reclaimed to greatest extent, turns waste into wealth, economize on resources, protection of the environment, started FeCl
3the new way of producing.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and following examples are intended to the present invention is described and can not be regarded as limitation of the invention.
Embodiment 1
By containing joining in the matrass of 1000ml in the crude titanic chloride precipitation mud 500ml of Ti14.3%, Al2.1%, Fe7.2%, then changing into 0.8 times of aluminum oxide stoichiometric number by aluminum contained compound and adding Fe
2o
3, 190 DEG C of atmospheric evaporations 4 hours, obtain TiCl
4steam and resistates; By TiCl
4steam-3 DEG C of liquid TiCl
4spray reclaims the TiCl obtained
4liquid; Then evaporation residue is transferred to corundum crucible 350 DEG C evaporation 3 hours, it is 98.6%FeCl that condensation obtains purity
3product.
Embodiment 2
The crude titanic chloride identical with embodiment 1 component is precipitated mud 200ml to be joined in the three-necked flask of 1500ml, then adds Fe by change into aluminum oxide stoichiometric number containing aluminium chlorine compound 1.5 times
2o
3, then 1:5 adds Skellysolve A by volume, stirs evenly rear clarification, removes supernatant liquor, then add Skellysolve A repeated washing once, filter containing TiCl
4solution and leach residue.Containing TiCl
4solution through 80 DEG C distillation 2 hours, vapour condensation obtains Skellysolve A liquid, evaporation residuum be thick TiCl
4liquid.Leach residue is first heated to 100 DEG C of reduction vaporizations 1 hour, the Skellysolve A etc. that volatilization is wherein residual, and be then warming up to 250 DEG C of reduction vaporizations 2.5 hours, it is 98.5%FeCl that condensation obtains purity
3product; The rate of recovery of whole technological process iron is 98.3%.
Embodiment 3
The crude titanic chloride identical with embodiment 1 component is precipitated mud 200ml to be joined in the three-necked flask of 1500ml, then adds Fe by change into aluminum oxide stoichiometric number containing aluminium chlorine compound 1.1 times
2o
3, then 1:1 adds monochlorethane by volume, stirs evenly rear clarification, removes supernatant liquor, then add monochlorethane repeated washing three times, filter containing TiCl
4solution and leach residue.Containing TiCl
4solution through 60 DEG C distillation 1.5 hours, vapour condensation obtains monochlorethane liquid, evaporation residuum be thick TiCl
4liquid.Leach residue adds dehydrated alcohol by solid-to-liquid ratio 1:6g/ml, agitation leach 10 hours, filters and obtains leached mud and contain FeCl
3filtrate.Containing FeCl
3filtrate through 200 DEG C of reduction vaporizations 3 hours, obtaining purity is 97.8%FeCl
3product.
Embodiment 4
By containing joining in the matrass of 1000ml in the titanium tetrachloride settling mud 200ml of Ti15.1%, Al0.5%, Fe8.1%, then changing into 2.8 times of aluminum oxide stoichiometric number by aluminum contained compound and adding Fe
2o
3, 110 DEG C of reduction vaporizations 2 hours, obtain TiCl
4steam and resistates; By TiCl
4steam-5 DEG C of liquid TiCl
4spray reclaims the TiCl obtained
4liquid; Resistates adds acetone by solid-to-liquid ratio 1:10g/ml, agitation leach 18 hours, filters and obtains leached mud and contain FeCl
3filtrate.Containing FeCl
3filtrate through 200 DEG C of reduction vaporizations 3 hours, obtaining purity is 98.1%FeCl
3product.
Claims (11)
1. a method for titanium tetrachloride settling mud synthetical recovery iron trichloride, comprises the steps:
The first step: remove in titanium tetrachloride settling mud containing aluminium chlorine compound
In crude titanic chloride precipitation mud, add the solid aluminium of ferric oxide, make the aluminium chlorine compound that contains wherein change into aluminum oxide, obtain solid aluminium titanium tetrachloride settling mud;
Second step: Separation and Recovery TiCl
4
Solid aluminium titanium tetrachloride settling mud is completely cut off air heating evaporation TiCl wherein
4, collection steam, condensation obtain titanium tetrachloride, and evaporation residue is for subsequent use; Or
Organic solvent (1) leaching TiCl wherein will added except aluminium titanium tetrachloride settling mud
4, filter containing TiCl
4solution and leach residue, containing TiCl
4solution again through distilling to obtain organic solvent (1) and TiCl
4;
3rd step: comprehensively recovering Fe Cl
3
The evaporation residue that second step is obtained or leach residue heating evaporation FeCl wherein
3, produce iron trichloride; Or
Organic solvent (2) is added, Selectively leaching FeCl wherein in the evaporation residue obtained at second step or leach residue
3, filter containing FeCl
3filtrate, containing FeCl
3filtrate again through distilling to obtain organic solvent (2) and iron trichloride.
2. the method for a kind of titanium tetrachloride settling mud synthetical recovery iron trichloride according to claim 1, is characterized in that: in the first step, and the ferric oxide added is that granularity is less than 60 object Fe
2o
3powder, Fe
2o
3addition by precipitation mud in AlCl
3all Al is transformed into AlOCl
2o
3the 0.5-5 amount doubly of chemical reaction stoichiometric number adds.
3. the method for a kind of titanium tetrachloride settling mud synthetical recovery iron trichloride according to claim 1 and 2, is characterized in that: in second step, and isolated air heating evaporation carries out under normal pressure or reduced pressure, and atmospheric evaporation temperature is 136-280 DEG C; Reduction vaporization temperature is 80-136 DEG C, and environmental stress is 0.09-0.1MPa.
4. the method for a kind of titanium tetrachloride settling mud synthetical recovery iron trichloride according to claim 1 and 2, it is characterized in that: in second step, described leaching is 1:0.25 ~ 25 mL/mL by volume, crude titanic chloride is precipitated mud and organic solvent (1) stirring and evenly mixing, make the TiCl carried secretly in mud
4enter organic solvent (1).
5. the method for a kind of titanium tetrachloride settling mud synthetical recovery iron trichloride according to claim 1 and 2, it is characterized in that: in second step, organic solvent (1) refer to containing 1 ~ 10 carbon atom, boiling point lower than 136 DEG C, be one or more in the hydrocarbon polymer of liquid or its chlorinated derivatives under normal temperature.
6. the method for a kind of titanium tetrachloride settling mud synthetical recovery iron trichloride according to claim 5, is characterized in that: organic solvent (1) is selected from least one in monochloro methane, methylene dichloride, trichloromethane, monochlorethane, ethylene dichloride, a chlorobutane, Skellysolve A, iso-pentane, normal hexane, isohexane, hexanaphthene.
7. the method for a kind of titanium tetrachloride settling mud synthetical recovery iron trichloride according to claim 1 and 2, is characterized in that: in second step, described to containing TiCl
4the distillation of solution is lower than at the temperature of 136 DEG C, and normal pressure or underpressure distillation, preferential evaporation organic solvent wherein (1), the organic solvent (1) that condensation obtains returns precipitation mud leaching TiCl
4operation recycles.
8. the method for a kind of titanium tetrachloride settling mud synthetical recovery iron trichloride according to claim 1 and 2, is characterized in that: in the 3rd step, FeCl described in heating evaporation
3be carry out under the condition of normal pressure or decompression, allow FeCl in evaporation residue or leach residue
3volatilization, condensation obtains iron trichloride; Atmospheric evaporation temperature is 280-500 DEG C; Reduction vaporization temperature is 150-280 DEG C, and environmental stress is 0.09-0.1MPa.
9. the method for a kind of titanium tetrachloride settling mud synthetical recovery iron trichloride according to claim 1 and 2, is characterized in that: in the 3rd step, and described organic solvent (2) is selected from one or more in methyl alcohol, ethanol, acetone.
10. the method for a kind of titanium tetrachloride settling mud synthetical recovery iron trichloride according to claim 1 and 2, is characterized in that: in the 3rd step, the FeCl described in Selectively leaching
3refer to by solid-to-liquid ratio 1:0.5 ~ 15g/mL, the evaporation residue obtained by second step or leach residue mix with organic solvent (2), and 0 ~ 80 DEG C is stirred 0.5 ~ 50h, Selectively leaching FeCl wherein
3, filter and obtain leached mud and contain FeCl
3filtrate.
The method of 11. a kind of titanium tetrachloride settling mud synthetical recovery iron trichlorides according to claim 1 and 2, is characterized in that: in the 3rd step, and described contains FeCl
3filtrate distillation is lower than at the temperature of 280 DEG C, and normal pressure or underpressure distillation, selectivity volatilization organic solvent wherein (2), the organic solvent (2) that condensation obtains returns FeCl
3leaching operation recycles.
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| CN103964496B (en) * | 2014-05-13 | 2015-09-30 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of titanium tetrachloride production system and technique |
| CN104891560B (en) * | 2015-05-19 | 2017-07-18 | 成都易态科技有限公司 | Crude titanic chloride production technology and its equipment |
| CN105502515B (en) * | 2016-01-18 | 2017-05-17 | 重庆科技学院 | Method for comprehensively recycling polymeric ferric aluminum chloride from titanium tetrachloride precipitate slurry |
| TWI637913B (en) * | 2017-12-08 | 2018-10-11 | 葉俊良 | Curing manufacturing method of hexahydrate ferric chloride and curing manufacturing system thereof |
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| EP2802675B1 (en) * | 2012-01-10 | 2020-03-11 | Orbite Aluminae Inc. | Processes for treating red mud |
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| CN102765749A (en) * | 2012-07-25 | 2012-11-07 | 中南大学 | Method for comprehensively recycling titanium and niobium from crude titanium tetrachloride precipitate mud |
| CN103145179A (en) * | 2013-03-22 | 2013-06-12 | 中南大学 | Method for recovering TiCl4 from titanium tetrachloride precipitation slurry |
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