CN102443710A - Method for treating scrapped molten salt generated in molten salt chlorination production method of TiCl4 - Google Patents
Method for treating scrapped molten salt generated in molten salt chlorination production method of TiCl4 Download PDFInfo
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- CN102443710A CN102443710A CN2011104200361A CN201110420036A CN102443710A CN 102443710 A CN102443710 A CN 102443710A CN 2011104200361 A CN2011104200361 A CN 2011104200361A CN 201110420036 A CN201110420036 A CN 201110420036A CN 102443710 A CN102443710 A CN 102443710A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention discloses a method for treating scrapped molten salt generated in the molten salt chlorination production method of TiCl4. The method comprises the following steps: directly keeping the temperature of the discharged scrapped molten salt at 500-900 DEG C, standing to ensure that the molten salt is divided into three layers, namely an upper layer (floating layer), a middle layer (molten salt layer) and a lower layer (precipitate layer), and then layering, wherein the upper layer is coke mixed with a little molten salt, and can be sent back to a molten salt chlorination furnace after separation for reuse, or can be used to recycle waste coke; and after deironing and demanganizing reduction treatment, the middle layer molten salt is cooled to the room temperature and treated with water and Na2CO3, thus the molten salt can be completely recycled and be used to produce Mn-Fe alloys (or Mn), MgCO3 and CaCO3 micropowder, AlCl3, SiCl4 and Cl2, the waste heat of the scrapped molten salt can be utilized, and the wastewater containing Cl<-> can be treated. Therefore, economic benefit and social benefit can be obtained.
Description
Technical field
The present invention relates to handle the method for waste fused salt, particularly relate to and handle fused salt chlorimation method production TiCl
4The method of the waste fused salt that produces.To the fused salt chlorimation abraum salt with contain Cl
-Waste water carry out the comprehensive regulation and utilization.
Background technology
Advantages such as metal titanium has that density is little, specific tenacity is high, anti-oxidant, antifatigue, erosion resistance are outstanding 26S Proteasome Structure and Function materials, enjoy " all-round metal ", " marine metal " and good reputations such as " metals of 21 century ".Be able to use widely in fields such as national defence, aerospace, navigation, oil, chemical industry, medical treatment, metallurgy.
White titanium pigment is a kind of white inorganic pigment; Have best opacity, best whiteness and luminance brightness and characteristic such as nontoxic; Generally acknowledged it is the present best white pigment of performance in the world, be widely used in industry such as coating, plastics, papermaking, printing-ink, chemical fibre, rubber, makeup.
TiCl
4Being the raw material of producing Titanium Sponge 40-60 mesh and chlorination production titanium white, also is preparation titanic acid ester and high-purity Ti O
2The raw material of super-fine powder.Industry is at present gone up and is produced TiCl
4Method two kinds of fluidizing chlorination and fused salt chlorimations are arranged:
Fluidizing chlorination: the compound of titanium slag and refinery coke is in fluidizing furnace and Cl
2Gas is in and carries out chlorination reaction under the fluidised state.Because gas and solid are in the relative movement of fierceness, mass transfer, heat transfer are well strengthened greatly and produced, and do not have briquetting, coking process, and be simple to operate continuous.
Fused salt chlorimation: be that titanium slag and refinery coke are suspended in the fused-salt medium, and Cl
2Solid/liquid/gas reactions generates TiCl
4The fused salt chlorimation method has following advantage:
(1) powder is gone into stove, and the granularity of raw material is not had harsh requirement.Than shaft chlorination and shaft chlorination continuously, saved briquetting and coking process, thereby simplified the preparatory technology of furnace charge;
(2) vigorous stirring in the molten salt body has been strengthened the process of triphasic heat transfer of solid-liquid-gas and mass transfer, thereby the specific productivity of stove is high.And TiCl
4Mud is easy to return the chlorination furnace recycling;
(3) almost be CO entirely because of what generate
2, and CO content is few, concentration in the furnace gas (dividing potential drop) increases, and helps the cooling of follow-up system, condensation process;
(4) than other several methods, process is carried out at a lower temperature, and the chloride concentration of iron, aluminium, silicon is low in the furnace gas, helps TiCl
4Refining purification;
(5) because the main CO that generates
2, rather than CO, even bled air, there is not explosion hazard yet, produce safer;
Biggest advantage is not harsh to the requirement of furnace charge, suitable treatment high calcium magnesium titanium slag and TiO
2The titanium slag that grade is lower.
But also there are some shortcomings in fused salt chlorimation, mainly is:
(1) big (the every production 1tTiCl of waste fused salt amount
4, produce waste fused salt 100-200kg approximately), its processing is difficulty relatively, and owing to want frequent salt discharge, can cause the loss of titanium and carbon;
(2) waste fused salt can not be handled and store up for a long time, and contained harmful muriate does not cause environmental pollution unavoidably;
Because the fused salt chlorimation method is to the wide accommodation of raw material, quality product is excellent, the TiCl of production
4Account for about 40% of present world titanium industry consumption.The geographic schreyerite in Flos Bombacis Malabarici-Xichang of China after treatment, in the gained titaniferous material, the content of calcium magnesium is higher, and (MgO+CaO ≧ 5-9%) is fit to adopt the fused salt chlorimation method to produce TiCl
4But when producing Titanium Sponge 40-60 mesh and white titanium pigment, in the fused salt chlorimation production process, can produce a large amount of fused salt waste residues, fused salt waste residue complicated component, stacking takies a large amount of places, heavy contamination.The abraum salt waste residue is that TiCl is produced in fused salt electrolysis
4Biggest obstacle, have a strong impact on the development of fused salt electrolysis process, comprehensive treating process and to utilize the abraum salt waste residue be that fused salt electrolysis process is produced TiCl
4The problem that needs to be resolved hurrily, if can successful processing and fully utilize the abraum salt waste residue, fused salt electrolysis process be produced TiCl
4With being endowed new life, its advantage can compare favourably with the fluidizing chlorination method fully.
Because abraum salt waste residue staple is a muriate, as deals with improperly, produce the chloride-sublimation hydrolysis, will cause the deterioration of waters, edatope on every side, cause the loss waste of wherein measuring useful resources simultaneously.Abroad be with after the water-soluble filtration of chloride slag; Gained filtrating is annotated people 1600m with sub-surface through special underground filling system; Although be perfused with the suitable degree of depth, yet in case geological movement takes place, may polluted underground water system even cause the pollution of face of land ecotope.External other, the landfill that the fused salt waste residue has is gone into the abandoned mine well, the employing that has with lime yard at a distance from lay in the wasteland; Domestic is to take lime to stir neutralizing treatment to stack the slag field again, and these methods all exist potential to pollute, like polluted underground water; Salinization soils etc. do not tackle the problem at its root.If can fundamentally solve waste fused salt stores up for a long time, contained harmful muriate does not cause environmental pollution problems unavoidably, and fused salt electrolysis process prepares TiCl
4Have incomparable meliority, can shine new life.
Summary of the invention
The object of the present invention is to provide a kind of processing fused salt chlorimation method to produce TiCl
4The method of the waste fused salt that produces.To the fused salt chlorimation abraum salt with contain Cl
-Waste water carry out the comprehensive regulation and utilization, solve fused salt electrolysis process and prepare TiCl
4The waste fused salt that exists is stored up for a long time, is harmful to the muriate contaminate environment and contains Cl
-The difficult problem of wastewater treatment.
The objective of the invention is to realize through following technical scheme:
Handle the fused salt chlorimation method and produce TiCl
4The method of the waste fused salt that produces, this method comprises following process: after waste fused salt is come out of the stove it is incubated and leaves standstill processing, the waste fused salt of coming out of the stove is incubated under 500-900 ℃ condition left standstill 5-90 minute; Make waste fused salt be divided into three layers, promptly the upper strata is floating layer, and the middle level is that molten salt layer and lower floor are the beds of precipitation; Successively separate then, after the separation, the upper strata is that coke is mixed with a spot of fused salt; Under the pyritous condition, directly return the fused salt chlorimation stove and reuse, or reclaim coke; The fused salt in middle level is realized waste fused salt regeneration and recycle, and is reclaimed Mn-Fe alloy, CaCO after handling through deironing, demanganization, demagging, deliming
3And MgCO
3Micro mist, AlCl
3Or SiCl
4, utilize the waste heat of waste fused salt and processing to contain Cl
-Waste water; Lower floor is the oxide compound that is mixed with small amount of chloride.
Described processing fused salt chlorimation method is produced TiCl
4The method of the waste fused salt that produces, described floating layer is for swimming in the coke that the fused salt upper surface is mixed with fused salt, and floating layer separates the back under hot conditions from fused salt, and it is multiplexing directly to return the fused salt chlorimation stove, or reclaims coke; The middle level is a molten chloride, and its composition is MgCl
2, NaCl, CaCl
2, KCl, manganese and iron heavy metal muriate, the molten chloride in middle level is with after separate the upper and lower, adds the iron that reductive agent removes and the muriate of manganese, reclaims the Mn-Fe alloy simultaneously, in dust-removal system, collects AlCl
3Or SiCl
4To remove behind the fused salt cool to room temperature of manganese and iron chloride brokenly then, and add entry and form supersaturated solution, supersaturated solution will be heated to 20-100 ℃; Form the insolubles and the aqueous solution; After filtering, in insolubles, isolate the solid of rich NaCl, in the aqueous solution, add Na
2CO
3, separate out MgCO in the cooling rear solution
3And CaCO
3Micro mist, behind the filtration micro mist, remainder water solution obtains the mixture of NaCl and KCl after evaporation is anhydrated; Or, recycle the fused salt formation supersaturated solution after the remainder water solution adding fragmentation.
Described processing fused salt chlorimation method is produced TiCl
4The method of the waste fused salt that produces, the muriatic reductive agent of described removal manganese and iron have aluminium system, silicon system, sial, manganese aluminium system and chlorine-aluminium system; Aluminium system comprises aluminium powder, aluminium scrap and scrap aluminium alloy, in dust-removal system, collects aluminum chloride; Silicon system comprises silica flour, silicon calcium powder and ferrosilicon powder, in dust-removal system, collects silicon chlorides; Sial system is meant at first reduces with ferrosilicon powder, with the reduction of aluminium based material, collects aluminum chloride and silicon chlorides in the dust-removal system respectively then; Chlorine-aluminium system uses earlier chlorine oxidation FeCl
2, make it change FeCl into
3With chlorine volatilization deironing, adding aluminium then is the reductive agent demanganization; Manganese aluminium system is meant at first and reduces with manganese metal or manganeseirom, with the reduction of aluminium based material, only collects aluminum chloride in the dust-removal system then, obtains alumal.
Described processing fused salt chlorimation method is produced TiCl
4The used heat that the method for the waste fused salt that produces, the fused salt behind described removal manganese and the iron chloride are emitted from high temperature cooling to the room temperature process is used for insulation, the heating of waste fused salt supersaturated aqueous solution and the evaporation of solution of waste fused salt.
Described processing fused salt chlorimation method is produced TiCl
4The method of the waste fused salt that produces, the fused salt cool to room temperature of described removal manganese and iron chloride is after fragmentation adds entry and forms supersaturated solution, and water is process water or contains Cl
-Waste water.
Advantage of the present invention and effect:
The present invention can thoroughly solve the fused salt chlorimation legal system and be equipped with TiCl
4The waste fused salt that exists can not be handled and store up for a long time, the difficult problem of harmful muriate contaminate environment, and the present invention can reclaim coke, muriate (mainly consisting of NaCl) fused salt mixt in the muriate abraum salt, produce Mn-Fe alloy (or metal M n), CaCO
3And MgCO
3Micro mist, AlCl
3(or SiCl
4), utilize the waste heat of waste fused salt and processing to contain Cl
-Waste water, realize the recycle of waste fused salt, bring considerable economic benefit and social benefit.
The present invention can realize the recovery and reuse of metal, has simple, the environmental protection advantage of technology.The present invention directly is incubated the waste fused salt of coming out of the stove to leave standstill under 500-900 ℃ condition; Make the melt of waste fused salt be divided into three layers; Be upper strata (floating layer); Middle level (molten salt layer) and lower floor's (beds of precipitation), the upper strata is the coke that is mixed with a small amount of fused salt, can directly return the fused salt chlorimation stove after the separation and reuse; The fused salt in middle level through art breading such as deironing, demanganization, demagging, delimings after, realize waste fused salt regeneration and recycle, and recyclable Mn-Fe alloy, CaCO
3And MgCO
3Micro mist, AlCl
3(or SiCl
4), utilize the waste heat of waste fused salt and processing to contain Cl
-Waste water.
Description of drawings
Fig. 1 is for handling embodiment 1 process flow sheet of waste fused salt;
Fig. 2 is for handling embodiment 2 process flow sheets of waste fused salt;
Fig. 3 is for handling embodiment 3 process flow sheets of waste fused salt;
Fig. 4 is for handling embodiment 4 process flow sheets of waste fused salt;
Fig. 5 is for handling embodiment 5 process flow sheets of waste fused salt.
Embodiment
With reference to the accompanying drawings the present invention is elaborated.
Embodiment 1:
As handle shown in technical process Fig. 1 of waste fused salt, the waste fused salt of coming out of the stove directly is incubated under 500-900 ℃ condition left standstill 5-120 minute, make waste fused salt be divided into three layers, i.e. upper strata (floating layer), middle level (molten salt layer) and lower floor's (beds of precipitation).
The upper strata is the coke that is mixed with a small amount of fused salt, and the upper strata is separated the back with the middle level and under the pyritous condition, directly returned fused salt chlorimation stove multiplexing (accounting for the 13.0-16.0% of fused salt gross weight) with lower floor, or reclaims coke.
The middle level is mainly muriatic fused salt, and its composition is mainly MgCl
2, KCl, CaCl
2, NaCl and manganese and iron muriate (accounting for the 70.0-74.0% of fused salt gross weight).
Lower floor's (beds of precipitation) is for being mixed with the oxide compound of small amount of chloride, and its staple is Al
2O
3, SiO
2, Fe
2O
3, TiO
2, CaO, MgO and a spot of muriate, account for the 10.0-17.0% of fused salt gross weight), add and can directly stack the slag field after 3.0% lime stirs neutralizing treatment.
The muriate in middle level (molten salt layer), its composition MgCl
2+ KCl+CaCl
2The muriate that+NaCl accounts for 76.0-80.0%, manganese and iron accounts for 20.0-24.0%; Under 500-800 ℃ condition; The aluminium powder (or industrial waste alumina and scrap aluminium alloy fragment) that adds the 2.5-4.5% that accounts for fused salt weight, after stirring the muriate of removing manganese and iron, MgCl in the fused salt
2, KCl, CaCl
2Can reach 95.0-98.0% with the content of NaCl; Impurity is FeCl
3, MnCl
3, AlCl
3With a spot of oxide compound, then with the fused salt cool to room temperature.This process can reclaim Mn-Fe alloy (Mn content is 50.0-70.0%) in the fused salt bottom, collects AlCl through dust-removal system
3
Get 100g then and remove to cool off the broken fused salt in back, add in the 45-70ml water and process supersaturated solution, be heated to 25-100 ℃ then, form the insolubles and the aqueous solution, after the filtration, in insolubles, isolate 45.3-52.5g NaCl; Add 40g Na2CO3 in the aqueous solution, the cool to room temperature after-filtration makes 34.0-38.2g MgCO
3And CaCO
3Micro mist; Remainder water solution obtains NaCl and the KCl of 9.1-12.3g after evaporation dewaters, the required energy of the heating of waste fused salt supersaturated solution and the evaporation of the aqueous solution is provided by other waste cell melt cooling.
Embodiment 2:
As handle shown in technical process Fig. 2 of waste fused salt, waste fused salt is after the insulation layering is handled, and the muriate composition of molten salt layer is: MgCl
2+ KCl+CaCl
2The muriate that+NaCl accounts for 76.0-80.0%, manganese and iron accounts for 20.0-24.0%; Add silicocalcium powder (or itself and the combination of silicon and ferro-silicon alloy powder) removal manganese and the iron chloride of the 2.5-3.5% of fused salt weight, from crucible, pour out the waste fused salt cool to room temperature then.The recyclable Mn-Fe alloy of this technology (Mn content is 45.0-70.0%) is collected SiCl through dust-removal system
4, after demanganization, the deironing, the MgCl of fused salt
2, KCl, CaCl
2With the content of NaCl be 95.3-98.0%.
Get the broken fused salt in 100g cooling back then, adding 45ml-70ml contains the waste water of 10000ppmCl-and processes supersaturated solution, is heated to 25-100 ℃, forms the insolubles and the aqueous solution, in insolubles, isolates 45.8-53.3g NaCl; In the aqueous solution, add 40g Na then
2CO
3, separate out 34.2-38.6g MgCO behind the cool to room temperature
3And CaCO
3Micro mist; The waste fused salt that remainder water solution adds after the fragmentation is again directly prepared supersaturated solution, the heating of waste fused salt supersaturated solution and the waste fused salt of coming out of the stove directly under 500-900 ℃ condition the required portion of energy of insulation provide by other waste cell melt cooling.
Embodiment 3:
As handle shown in technical process Fig. 3 of waste fused salt; Its technical process and instance two are basic identical; Difference is: at first add the silica flour (or ferro-silicon alloy powder) of the 1.0-2.5% of fused salt weight in the fused salt of middle level, remove the muriate of iron, take out the metallic iron of crucible bottom; The aluminium powder (or industrial waste alumina and scrap aluminium alloy powder) that adds the 1.0-2.5% of fused salt weight again can reclaim metal M n (Mn content is greater than 90.0%) in the fused salt bottom, collects AlCl through dust-removal system
3And SiCl
4, this technology removal manganese and iron chloride are more complete, handle MgCl in the fused salt of back
2, KCl, CaCl
2Reach 96.0-98.5% with the content of NaCl.
Embodiment 4:
As handle shown in technical process Fig. 4 of waste fused salt, its technical process and instance three are basic identical, and difference is: feed the chlorine of lower concentration in the fused salt of middle level earlier, remove the muriate of iron; The aluminium that adds the 1.0-2.0% of fused salt weight again is reductive agent, can reclaim metal M n (Mn content is greater than 85.0%) in the fused salt bottom, collects FeCl through dust-removal system
3, behind the muriate of removal iron and manganese, MgCl in the fused salt
2, KCl, CaCl
2Reach 96.0-97.5% with the content of NaCl.
Embodiment 5:
As handle shown in technical process Fig. 5 of waste fused salt; Its technical process and instance three are basic identical, and difference is: the middle level fused salt at first adds the normal manganese powder of 1.05-1.5 iron in fused salt under 670-1100 ℃ condition; Remove the muriate of iron, take out the metallic iron of crucible bottom; Add 1.0-500 times of normal metallic aluminium of manganese in the fused salt again; Stirred 0.5 hour; Fused salt and Al-Mn alloy are cooled off together, can reclaim Al-Mn (Mn content>5.0%) after the cooling, collect AlCl3 through dust-removal system in fused salt bottom; This technology removal manganese and iron chloride are more complete, and the content of handling MgCl2, KCl, CaCl2 and NaCl in the fused salt of back reaches 96.0-98.5%.Behind the separation Al-Mn alloy that waste fused salt is broken.
Add in the waste fused salt that to account for muriate quality 45.0-70.0% concentration be the waste water of the Cl-of 10000ppm; Formation temperature is 80-100 ℃ a muriate supersaturated solution; Isolate the muriate saturated solution of NaCl solid and heat after the filtration, isolated NaCl accounts for the 35.0-42.0% of waste fused salt gross weight; At first add milk of lime in the muriate saturated solution of thermotropism, adjustment PH>10.9, obtain throw out and solution, the content of Mg in the throw out (OH) 2>95.3%; In the aqueous solution, add then with solution in the Na2CO3 of Ca2+ equivalent; Behind cold filtration; Isolate the aqueous solution of solid phase, NaCl and KCl; Solid phase is a purity greater than 96.0% CaCO3 micro mist, and the aqueous solution of NaCl and KCl adds the muriate supersaturated solution that muriate after the fragmentation is processed heat, recycles.
Claims (5)
1. handle the fused salt chlorimation method and produce TiCl
4The method of the waste fused salt that produces is characterized in that, this method comprises following process: after waste fused salt is come out of the stove it is incubated and leaves standstill processing; The waste fused salt of coming out of the stove is incubated under 500-900 ℃ condition left standstill 5-90 minute, make waste fused salt be divided into three layers, promptly the upper strata is floating layer; The middle level is that molten salt layer and lower floor are the beds of precipitation, successively separates then, after the separation; The upper strata is that coke is mixed with a spot of fused salt, under the pyritous condition, directly returns the fused salt chlorimation stove and reuses, or reclaim coke; The fused salt in middle level is realized waste fused salt regeneration and recycle, and is reclaimed Mn-Fe alloy, CaCO after handling through deironing, demanganization, demagging, deliming
3And MgCO
3Micro mist, AlCl
3Or SiCl
4, utilize the waste heat of waste fused salt and processing to contain Cl
-Waste water; Lower floor is the oxide compound that is mixed with small amount of chloride.
2. processing fused salt chlorimation method according to claim 1 is produced TiCl
4The method of the waste fused salt that produces is characterized in that, described floating layer is for swimming in the coke that the fused salt upper surface is mixed with fused salt, and floating layer separates the back under hot conditions from fused salt, and it is multiplexing directly to return the fused salt chlorimation stove, or reclaims coke; The middle level is a molten chloride, and its composition is MgCl
2, NaCl, CaCl
2, KCl, manganese and iron heavy metal muriate, the molten chloride in middle level is with after separate the upper and lower, adds the iron that reductive agent removes and the muriate of manganese, reclaims the Mn-Fe alloy simultaneously, in dust-removal system, collects AlCl
3Or SiCl
4To remove behind the fused salt cool to room temperature of manganese and iron chloride brokenly then, and add entry and form supersaturated solution, supersaturated solution will be heated to 20-100 ℃; Form the insolubles and the aqueous solution; After filtering, in insolubles, isolate the solid of rich NaCl, in the aqueous solution, add Na
2CO
3, separate out MgCO in the cooling rear solution
3And CaCO
3Micro mist, behind the filtration micro mist, remainder water solution obtains the mixture of NaCl and KCl after evaporation is anhydrated; Or, recycle the fused salt formation supersaturated solution after the remainder water solution adding fragmentation.
3. processing fused salt chlorimation method according to claim 1 is produced TiCl
4The method of the waste fused salt that produces is characterized in that, the muriatic reductive agent of described removal manganese and iron has aluminium system, silicon system, sial, manganese aluminium system and chlorine-aluminium system; Aluminium system comprises aluminium powder, aluminium scrap and scrap aluminium alloy, in dust-removal system, collects aluminum chloride; Silicon system comprises silica flour, silicon calcium powder and ferrosilicon powder, in dust-removal system, collects silicon chlorides; Sial system is meant at first reduces with ferrosilicon powder, with the reduction of aluminium based material, collects aluminum chloride and silicon chlorides in the dust-removal system respectively then; Chlorine-aluminium system uses chlorine oxidation FeCl2 earlier, makes it change FeCl3 into the chlorine deironing of volatilizing, and adding aluminium then is the reductive agent demanganization; Manganese aluminium system is meant at first and reduces with manganese metal or manganeseirom, with the reduction of aluminium based material, only collects aluminum chloride in the dust-removal system then, obtains alumal.
4. processing fused salt chlorimation method according to claim 1 is produced TiCl
4The method of the waste fused salt that produces is characterized in that, the used heat that the fused salt behind described removal manganese and the iron chloride is emitted from high temperature cooling to the room temperature process is used for insulation, the heating of waste fused salt supersaturated aqueous solution and the evaporation of solution of waste fused salt.
5. processing fused salt chlorimation method according to claim 1 is produced TiCl
4The method of the waste fused salt that produces is characterized in that, the fused salt cool to room temperature of described removal manganese and iron chloride is after fragmentation adds entry and forms supersaturated solution, and water is process water or contains Cl
-Waste water.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011203A (en) * | 2012-12-07 | 2013-04-03 | 沈阳化工大学 | Method for treatment of chlorinated waste molten salt generated in TiCl4 production process |
| CN103834989A (en) * | 2014-02-24 | 2014-06-04 | 锦州钛业有限公司 | Process of producing calcium sulfate crystal whiskers from chloride-containing wastewater generated in chloride process titanium dioxide production |
| CN104198654A (en) * | 2014-08-15 | 2014-12-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for determining fused salt components in production process of titanium tetrachloride by fused salt chlorination method |
| CN104911635A (en) * | 2015-05-05 | 2015-09-16 | 中国科学院过程工程研究所 | Method for alkali recovery and molten salt circulation in electrolytic process of refractory metal oxacid salt |
| CN111892068A (en) * | 2020-08-13 | 2020-11-06 | 中南大学 | Method for treating fused salt chlorination waste residue by high-temperature phase conversion method |
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| CN114672849A (en) * | 2022-04-29 | 2022-06-28 | 中国原子能科学研究院 | Rapid casting method of molten salt electrolysis metal |
| CN115504494A (en) * | 2022-09-14 | 2022-12-23 | 江苏柏环环境科技有限公司 | Salt-containing solid waste resource recovery method |
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| CN103011203A (en) * | 2012-12-07 | 2013-04-03 | 沈阳化工大学 | Method for treatment of chlorinated waste molten salt generated in TiCl4 production process |
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| CN104911635A (en) * | 2015-05-05 | 2015-09-16 | 中国科学院过程工程研究所 | Method for alkali recovery and molten salt circulation in electrolytic process of refractory metal oxacid salt |
| CN111892068A (en) * | 2020-08-13 | 2020-11-06 | 中南大学 | Method for treating fused salt chlorination waste residue by high-temperature phase conversion method |
| CN111892068B (en) * | 2020-08-13 | 2021-11-02 | 中南大学 | Method for treating fused salt chlorination waste residue by high-temperature phase conversion method |
| CN114393666A (en) * | 2022-03-01 | 2022-04-26 | 南京林业大学 | Preparation method of glue-free bamboo fiber product |
| CN114672849A (en) * | 2022-04-29 | 2022-06-28 | 中国原子能科学研究院 | Rapid casting method of molten salt electrolysis metal |
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