CN103011203B - Method for treatment of chlorinated waste molten salt generated in TiCl4 production process - Google Patents
Method for treatment of chlorinated waste molten salt generated in TiCl4 production process Download PDFInfo
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- CN103011203B CN103011203B CN201210521732.6A CN201210521732A CN103011203B CN 103011203 B CN103011203 B CN 103011203B CN 201210521732 A CN201210521732 A CN 201210521732A CN 103011203 B CN103011203 B CN 103011203B
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Abstract
Relating to comprehensive treatment and utilization methods of chlorinated molten salts, the invention discloses a method for treatment of a chlorinated waste molten salt generated in a TiCl4 production process. The method consists of: discharging a waste molten salt generated during TiCl4 production from a furnace, cooling the salt, and subjecting it to layered crushing, leaving the chlorinated waste molten salt to undergo a water dissolution treatment to prepare an NaCl-containing solution, separating residue and a chloride to conduct treatment, removing iron, manganese and chromium, carrying out filtration to obtain residue and a supernatant, adding an alkali solution into the supernatant to separate a precipitate, and conducting washing to remove Cl<-> so as to obtain a magnesium product and a supernatant, treating the magnesium product to prepare a magnesium hydroxide flame retardant or active magnesium oxide, then adding sodium carbonate into the supernatant to obtain calcium carbonate micro-powder and a high purity NaCl solution, and treating the calcium carbonate micro-powder and the NaCl solution respectively, thus realizing comprehensive utilization of the waste molten salt. The method disclosed in the invention solves the waste molten salt and Cl<-> containing wastewater environmental pollution problem plaguing the molten salt chlorination preparation method of TiCl4 for a long term.
Description
Technical field
The present invention relates to the method to the comprehensive regulation of chlorination fused salt and utilization, particularly relate to a kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process.
Background technology
Fused salt chlorimation legal system is for TiCl
4the wide accommodation of maximum advantage to raw material, suitable treatment high calcium magnesium titanium slag and TiO
2the titanium slag that grade is lower, product quality excellence, the TiCl of production
4account for 40% left and right of current World Titanium industry consumption.After treatment, in gained titaniferous material, the content of calcium magnesium higher (MgO+CaO≤5-9%), is applicable to adopting fused salt chlorimation method to produce TiCl to the schreyerite of the Panzhihua-Xichang Region of China
4.But in producing titanium sponge and titanium dioxide, in fused salt chlorimation production process, can produce a large amount of fused salt waste residues, abraum salt waste residue main component is chloride, as deal with improperly, the hydrolysis of generation chloride-sublimation, to cause the deterioration of waters, soil environment around, cause simultaneously the loss waste of wherein measuring useful resources.Abroad by after water-soluble chloride slag filtration, gained filtrate is noted people 1600m with sub-surface by special underground filling system, although be perfused with the suitable degree of depth, once but generation geological movement may polluted underground water be the pollution that even causes surface environment.External other, the landfill that fused salt waste residue has enters abandoned mine well, some employings with lime yard every lay in wasteland, domestic is to take lime to stir neutralisation treatment to pile slagging field again, all there is potential pollution in these methods, as polluted underground water, salinization soil etc., does not tackle the problem at its root.
Magnesium hydroxide belongs to addition type inorganic combustion inhibitor, compare with similar inorganic combustion inhibitor, macromolecular material is obtained outside good flame retardant effect, can also suppress the generation of the poisonous gas such as smog and hydrogen halides, there is better smoke suppressing effect, be magnesium hydroxide remove have fire-retardant, eliminate smoke and fill triple functions, give material non-toxic, non-corrosiveness simultaneously.Magnesium hydroxide is all unharmful substance discharges in the process of production, use and generation of waste materials, and environment is not polluted.Decomposition temperature is high, can be composite with Multiple components.And thering is acid-resisting, the acidity and the corrosive gas that in energy, produce with combustion process, be a kind of environmentally friendly Green Flammability agent.
Nano-calcium carbonate, after surface modification, can be used as a kind of functional filler and is applied in widely the fields such as plastics, rubber, papermaking, fluid sealant.
China is that the big producing country of calcium carbonate product is in the world also consumption big country, and annual production now can reach 4,000,000 tons.Japan all has state-of-the-art calcium carbonate production technology all the time, and a series of calcium carbonate that they produce and modified calcium carbonate product are all in world lead level; The U.S. biases toward production papermaking and coating calcium carbonate product: Britain is partial to study the calcium carbonate adding in automobile making plastics used, and Germany biases toward the research of filler calcium carbonate product.Although the potentiality of China's calcium carbonate industry are larger, product specification is lower, and some high-grade calcium carbonate products still need import.
Summary of the invention
The object of the present invention is to provide a kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process.The present invention utilizes chlorination waste fused salt for raw material, reclaims the raw materials such as coke, sodium chloride, and prepares CaCO
3micro mist and flame retardant of magnesium hydroxide, realize the comprehensive utilization of waste fused salt, solves long-term puzzlement fused salt electrolysis process and prepare TiCl
4the waste fused salt existing and containing Cl
-the problem of contaminated wastewater environment.
The object of the invention is to be achieved through the following technical solutions:
A kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process, described method comprises following process: produce TiCl
4the waste fused salt producing come out of the stove cooling after, by its layering fragmentation, chlorination waste fused salt, through water-soluble processing, is prepared into the supersaturated solution that is rich in NaCl, separate after slag and the aqueous solution, slag and the chloride that is dissolved in water are processed respectively, tentatively carried out deironing, demanganization, dechromisation, after filtration, obtain residue and supernatant, then supernatant is carried out to smart removal of impurities, filtration residue then adds alkali lye in supernatant, isolates sediment and washing removal Cl
-after, obtain magnesium goods and supernatant, magnesium goods are processed, prepare flame retardant of magnesium hydroxide and light magnesium oxide, in backward supernatant, add sodium carbonate, obtain the NaCl solution that calcium carbonate fine powder and purity are higher, then respectively to calcium carbonate fine powder and NaCl solution-treated, realize the comprehensive utilization of waste fused salt.
Described a kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process, chlorination waste fused salt, through water-soluble processing, is prepared into the supersaturated solution that is rich in NaCl, separates after slag and the aqueous solution, adds NaOH to process slag, and neutralization is that 7 rear press filtrations are dried to pH, obtains thick NaCl.
Described a kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process, adds OH by the chloride that is dissolved in water
-carry out deironing, demanganization and dechromisation processing, introduce OH
-mode be NaOH, milk of lime and combination thereof.
Described a kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process, in removal supernatant, Mn, the Fe of remnants, the mode of Cr ion are in supernatant, to add reducing agent sodium hydrosulfite, make to be dissolved in Mn, Fe, Cr ion in solution, thoroughly remove with the form of metal M n, Fe, Cr; Or add the mode of oxidant by Fe
2+, Mn
2+be oxidized to Fe
3+and Mn
3+, make it generate Fe(OH)
3and Mn(OH)
3precipitation is removed, and the oxidant adding has H
20
2or air, then add Fe powder or reducing agent sodium hydrosulfite to remove the chromium in solution; Or directly add the Cr VI in iron powder, sodium hydrosulfite reducing solution, then use complexing agent ethylenediamine tetra-acetic acid (EDTA) and the removal of impurity of reducing agent sodium hydrosulfite.
Described a kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process adds NaOH solution in supernatant, is settled out magnesium hydroxide.By the magnesium hydroxide being settled out, with after complexing agent ethylenediamine tetra-acetic acid (EDTA) and the removal of impurity of reducing agent sodium hydrosulfite, filtrate adds ammoniacal liquor to carry out aminating reaction, produces fire retardant magnesium hydroxide.
Described a kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process, or add milk of lime in supernatant, by the sediment of magnesium hydroxide and calcium hydroxide, then pass into CO
2, obtain heavy magnesium water Mg(HCO
3)
2filtrate, the filtrate of heavy magnesium water, filtrate adds ammoniacal liquor to carry out aminating reaction, prepares magnesium hydroxide.
Described a kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process, is rich in the magnesium hydroxide of impurity, after filtering and cleaning, then uses complexing agent ethylenediamine tetra-acetic acid (EDTA) and the removal of impurity of reducing agent sodium hydrosulfite, and filter residue is passed into CO
2gas carries out carburizing reagent, add crystal control agent, coating material and dispersant simultaneously, generate magnesium bicarbonate and the lime deposit of solubilised state, through press filtration, filter cake is for containing magnesium calcium carbonate, and filtrate can be produced fire retardant magnesium hydroxide, basic magnesium carbonate and magnesia.
Described a kind of process for producing TiCl
4the method of the chlorination waste fused salt producing in process, adds sodium carbonate in supernatant, the calcium carbonate fine powder obtaining can directly be prepared calcium carbonate fine powder to calcium carbonate fine powder washing removal of impurities.Or calcium carbonate fine powder calcining is generated to quick lime, and adding water and digest and remove after impurity, logical people's carbon dioxide carries out carbonization, finally the slurries after carbonization is filtered, is dried and modification obtains nano-calcium carbonate calcium product.
Advantage of the present invention and effect are:
The present invention can solve long-term puzzlement fused salt chlorimation legal system for TiCl
4a difficult problem for the waste fused salt processing existing, recyclable sodium chloride, the valuable elements such as Mn, Fe, preparation CaCO
3micro mist (or nanometer CaCO
3) and Mg (OH)
2the raw materials such as fire retardant (or basic magnesium carbonate and magnesia).
Brief description of the drawings
Fig. 1 is the technological process embodiment 1 that processes waste fused salt;
Fig. 2 is the technological process embodiment 2 that processes waste fused salt;
Fig. 3 is the technological process embodiment 3 that processes waste fused salt;
Fig. 4 is the technological process embodiment 4 that processes waste fused salt;
Fig. 5 is the technological process embodiment 5 that processes waste fused salt;
Fig. 6 is the technological process embodiment 6 that processes waste fused salt;
Fig. 7 is the technological process embodiment 7 that processes waste fused salt;
Fig. 8 is the technological process embodiment 8 that processes waste fused salt.
Detailed description of the invention
Below in conjunction with accompanying drawing illustrated embodiment, the present invention is described in detail.
Embodiment mono-: as shown in processing technological process Fig. 1 of waste fused salt, waste fused salt is direct cool to room temperature after coming out of the stove, then by waste fused salt layering fragmentation.Bottom is oxide skin(coating), is oxide and partial oxidation thing, and the main component of oxide is Al
2o
3, SiO
2, Fe
2o
3, TiO
2, CaO, MgO, account for the 13.0-15.0% of fused salt gross weight, in oxide skin(coating), contain the chloride of 10.3-30.5%; Top is coke layer; Middle part is chloride layer.To in oxide skin(coating), add industrial wastewater, make muriatic solution, after filtration, isolate solid phase and muriatic solution; In coke layer, add industrial wastewater, isolate coke and chloride solution, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
In chloride layer, add and account for chloride quality 45.0-90.0% water, formation temperature is the chloride supersaturated solution of 40-95 DEG C, after filtration, isolate NaCl solid and hot chloride saturated solution, isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight, add NaOH to neutralize after pH equals 7 isolated NaCl, after oven dry, can return molten salt furnace reuse; Then by chloride saturated solution, first add NaOH, adjust to pH=5.2, be precipitated thing and chloride solution, sediment is mainly Fe(OH)
3, through processing, can prepare Fe
2o
3(iron oxide red); Then regulate pH=7.0-7.8, add NaOH solution, make the Mn of chloride solution
2+and Fe
2+most of generation precipitated, and without Mg
2+precipitation, passes into air afterwards, makes to remain in the Mn in chloride solution
2+and Fe
2+be converted into Fe
3+and Mn
3+thereby, be converted into Fe(OH)
3and Mn(OH)
3precipitation, then adds reduced powder, makes heavy metal ion in chloride solution transform metallic atom and separates out, and the metal ion such as the Fe in chloride solution, Mn, Cr is removed substantially completely like this, Mn(OH)
2and Fe(OH)
2content be 28.3%-31.5%, remaining is compound and impurity in iron content, sediment separate after through thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add to add in the aqueous solution with solution in Mg
2+and Ca
2+the NaOH of equivalent, makes the Ca in solution
2+and Mg
2+be converted into Ca(OH completely)
2and Mg(OH)
2precipitation, after Separation of Solid and Liquid, filter residue is produced refining liquid through slagging-off, and the preparation dolomite ash breast that adds water, passes into CO
2adding the 0.1-0.6% Sodium Polyacrylate that accounts for magnesium calcium carbonate dry basic weight is dispersant, add and account for the 0.1-0.6% polyethylene glycol of magnesium calcium carbonate dry basic weight-be dressing agent, taking aluminum trichloride (anhydrous) (AlCl3) and ethylenediamine tetra-acetic acid (EDTA) as crystal control agent and dispersant, generate the magnesium bicarbonate of solubilised state and the calcium carbonate of precipitation, through press filtration, filter cake is for containing magnesium calcium carbonate, produces ultra-fine containing magnesium calcium carbonate product through surface modification, dry, classification, packaging.
Filtrate is reacted with ammoniacal liquor, generate magnesium hydroxide and carbonic hydroammonium, after isolated by filtration, magnesium hydroxide is prepared flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packaging again, and carbonic hydroammonium decomposes ammonification, carbon dioxide and water and can be recycled.
Continue to add and Ca in chloride solution
2+the Na of equivalent
2cO
3, after cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packaging
3.
The aqueous solution of part NaCl is sent into the raw material of chlor-alkali plant as chemical industry for making chlorine and alkali through processing.The aqueous solution of part NaCl and KCl evaporates through solvent, removes after water, extracts NaCl and KCl.By waste fused salt, cooling and muriatic heat of solution provides the required part heat of heating chloride solution.
Embodiment bis-: as shown in processing technological process Fig. 2 of waste fused salt, waste fused salt is direct cool to room temperature after coming out of the stove, then by waste fused salt layering fragmentation.Bottom is oxide skin(coating), is oxide and partial oxidation thing, and the main component of oxide is Al
2o
3, SiO
2, Fe
2o
3, TiO
2, CaO, MgO, account for the 13.0-15.0% of fused salt gross weight, in oxide skin(coating), contain the chloride of 10.3-30.5%; Top is coke layer; Middle part is chloride layer.To in oxide skin(coating), add industrial wastewater, make muriatic solution, after filtration, isolate solid phase and muriatic solution; In coke layer, add industrial wastewater, isolate coke and chloride solution, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
In chloride layer, add and account for chloride quality 45.0-90.0% water, formation temperature is the chloride supersaturated solution of 40-95 DEG C, isolates NaCl solid and hot chloride saturated solution after filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; By chloride saturated solution, first add milk of lime, adjust to pH=5.2, be precipitated thing and chloride solution, sediment is mainly Fe(OH)
3, after cleaning calcining, prepare iron oxide, then add milk of lime, regulate pH=6.0, make the Mn of chloride solution
2+and Fe
2+most of generation precipitated, and Mg
2+precipitation, does not pass into hydrogen peroxide afterwards, makes to remain in the Mn in chloride solution
2+and Fe
2+be converted into Fe
3+and Mn
3+thereby, be converted into Fe(OH)
3and Mn(OH)
3precipitation, then adds reduced powder, makes heavy metal ion in chloride solution transform metallic atom and separates out, and the metal ion such as the Fe in chloride solution, Mn, Cr is removed substantially completely like this, Mn(OH)
2and Fe(OH)
2content be 28.3%-31.5%, remaining compound and impurity such as be iron content, after sediment separates through cleaning, thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add in the aqueous solution with solution in Mg
2+the fat lime breast of equivalent, makes the Mg in solution
2+be converted into Mg(OH completely)
2precipitation, simultaneously Mg(OH)
2precipitation is also mixed with a small amount of Ca(OH)
2, after Separation of Solid and Liquid, filter residue is produced refining liquid through slagging-off, then the generation dolomite ash breast that adds water, then CO
2carry out carburizing reagent, generate magnesium bicarbonate and contain magnesium calcium carbonate, after calcium carbonate is removed in press filtration, mother liquor obtains basic magnesium carbonate through pyrolysis, the dry hydration basic magnesium carbonate that obtains again after filtration,, calcium carbonate filter cake drying obtains containing magnesium calcium carbonate, the wet basic magnesium carbonate that pyrolysis obtains after filtering, then drying calcining obtains industrial magnesium oxide.
Continue to add and Ca in chloride solution
2+the Na of equivalent
2cO
3octadecanol phosphate (ODP) dispersant, calgon is controlled at 1%～3% (crystal-directing-agent consumption accounts for the mass fraction of calcium carbonate solid amount) as the general consumption of crystalline form directed agents and selects crystal-directing-agent calgon, after cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packaging
3,
Embodiment tri-: as shown in processing technological process Fig. 3 of waste fused salt, waste fused salt is direct cool to room temperature after coming out of the stove, then by waste fused salt layering fragmentation.Bottom is oxide skin(coating), is oxide and partial oxidation thing, and the main component of oxide is Al
2o
3, SiO
2, Fe
2o
3, TiO
2, CaO, MgO, account for the 13.0-15.0% of fused salt gross weight, in oxide skin(coating), contain the chloride of 10.3-30.5%; Top is coke layer; Middle part is chloride layer.To in oxide skin(coating), add industrial wastewater, make muriatic solution, after filtration, isolate solid phase and muriatic solution; In coke layer, add industrial wastewater, isolate coke and chloride solution, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
In chloride layer, add and account for chloride quality 45.0-90.0% water, formation temperature is the chloride supersaturated solution of 40-95 DEG C, isolates NaCl solid and hot chloride saturated solution after filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; By chloride saturated solution, first add milk of lime, adjust to pH=5.2, be precipitated thing and chloride solution, sediment is mainly Fe(OH)
3, through processing, can prepare Fe
2o
3(iron oxide red), then regulates pH=6.0, continues to add milk of lime, makes the Mn of chloride solution
2+and Fe
2+most of generation precipitated, and without Mg
2+precipitation, passes into air afterwards, makes to remain in the Mn in chloride solution
2+and Fe
2+be converted into Fe
3+and Mn
3+thereby, be converted into Fe(OH)
3and Mn(OH)
3precipitation, then adds reduced powder, makes heavy metal ion in chloride solution transform metallic atom and separates out, and the metal ion such as the Fe in chloride solution, Mn, Cr is removed substantially completely like this, Mn(OH)
2and Fe(OH)
2content be 28.3%-31.5%, remaining is compound and impurity in iron content, sediment separate after through thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add to add in the aqueous solution with solution in Mg
2+and Ca
2+the ammoniacal liquor of equivalent, makes the Ca in solution
2+and Mg
2+be converted into Ca(OH completely)
2and Mg(OH)
2precipitation, after Separation of Solid and Liquid, filter residue is produced refining liquid through slagging-off, and the preparation dolomite ash breast that adds water, passes into CO
2adding the 0.1-0.6% Sodium Polyacrylate that accounts for magnesium calcium carbonate dry basic weight is dispersant, adding 0.1-0.6% polyethylene glycol one phosphoric acid that accounts for magnesium calcium carbonate dry basic weight is extremely dressing agent, taking aluminum trichloride (anhydrous) (AlCl3) and ethylenediamine tetra-acetic acid (EDTA) as crystal control agent and dispersant, generate the magnesium bicarbonate of solubilised state and the calcium carbonate of precipitation, through press filtration, filter cake is for containing magnesium calcium carbonate, produces ultra-fine containing magnesium calcium carbonate product through surface modification, dry, classification, packaging.
Filtrate is reacted with ammoniacal liquor, generate magnesium hydroxide and carbonic hydroammonium, after isolated by filtration, magnesium hydroxide is through hydrothermal treatment consists, magnesium hydroxide crystal growth, prepare flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packaging again, carbonic hydroammonium decomposes ammonification, carbon dioxide and water and can be recycled.
Continue to add and Ca in chloride solution
2+the Na of equivalent
2cO
3, after cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packaging
3, solution after treatment, is prepared Na by Hou Shi alkali-making process
2cO
3and NH
4cl.
Embodiment tetra-: as shown in processing technological process Fig. 4 of waste fused salt, waste fused salt is direct cool to room temperature after coming out of the stove, then by waste fused salt layering fragmentation.Bottom is oxide skin(coating), is oxide and partial oxidation thing, and the main component of oxide is Al
2o
3, SiO
2, Fe
2o
3, TiO
2, CaO, MgO, account for the 13.0-15.0% of fused salt gross weight, in oxide skin(coating), contain the chloride of 10.3-30.5%; Top is coke layer; Middle part is chloride layer.To in oxide skin(coating), add industrial wastewater, make muriatic solution, after filtration, isolate solid phase and muriatic solution; In coke layer, add industrial wastewater, isolate coke and chloride solution, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
In chloride layer, add and account for chloride quality 45.0-90.0% water, formation temperature is the chloride supersaturated solution of 40-95 DEG C, isolates NaCl solid and hot chloride saturated solution after filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; By chloride saturated solution, first add milk of lime, adjust to pH=5.2, be precipitated thing and chloride solution, sediment is mainly Fe(OH)
3, through processing, can prepare Fe
2o
3(iron oxide red), then regulates pH=6.0, continues to add milk of lime, makes the Mn of chloride solution
2+and Fe
2+most of generation precipitated, and without Mg
2+precipitation, passes into air afterwards, makes to remain in the Mn in chloride solution
2+and Fe
2+be converted into Fe
3+and Mn
3+thereby, be converted into Fe(OH)
3and Mn(OH)
3precipitation, then adds reduced powder, makes heavy metal ion in chloride solution transform metallic atom and separates out, and the metal ion such as the Fe in chloride solution, Mn, Cr is removed substantially completely like this, Mn(OH)
2and Fe(OH)
2content be 28.3%-31.5%, remaining is compound and impurity in iron content, sediment separate after through thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add to add in the aqueous solution with solution in Mg
2+the high-quality Ca(OH of equivalent)
2, make the Mg in solution
2+be converted into Mg(OH completely)
2precipitation, simultaneously Mg(OH)
2precipitation is also mixed with a small amount of Ca(OH)
2, after Separation of Solid and Liquid, filter residue is produced refining liquid through slagging-off, then the generation dolomite ash breast that adds water, then CO
2carry out carburizing reagent, generate magnesium bicarbonate and contain magnesium calcium carbonate, after calcium carbonate is removed in press filtration, filtrate is reacted with ammoniacal liquor, generate magnesium hydroxide and carbonic hydroammonium, after isolated by filtration, magnesium hydroxide is prepared flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packaging again, and carbonic hydroammonium decomposes ammonification, carbon dioxide and water and can be recycled.
Continue to add and Ca in chloride solution
2+the Na of equivalent
2cO
3, after cold filtration, solid phase obtains CaCO
3, be all that lime stone is calcined and generated quick lime, add water and digest and remove after impurity, logical people's carbon dioxide carries out carbonization, finally the slurries after carbonization is filtered, is dried and modification obtains nano-calcium carbonate calcium product.Solution after treatment, is prepared Na by Hou Shi alkali-making process
2cO
3and NH
4cl.
Embodiment five: as shown in processing technological process Fig. 5 of waste fused salt, waste fused salt is direct cool to room temperature after coming out of the stove, then by waste fused salt layering fragmentation.Bottom is oxide skin(coating), is oxide and partial oxidation thing, and the main component of oxide is Al
2o
3, SiO
2, Fe
2o
3, TiO
2, CaO, MgO, account for the 13.0-15.0% of fused salt gross weight, in oxide skin(coating), contain the chloride of 10.3-30.5%; Top is coke layer; Middle part is chloride layer.To in oxide skin(coating), add industrial wastewater, make muriatic solution, after filtration, isolate solid phase and muriatic solution; In coke layer, add industrial wastewater, isolate coke and chloride solution, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
In chloride layer, add and account for chloride quality 45.0-90.0% water, formation temperature is the chloride supersaturated solution of 40-95 DEG C, isolates NaCl solid and hot chloride saturated solution after filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; By chloride saturated solution, add lime milk solution, then regulate pH=7.0-7.8, make the Mn of chloride solution
2+and Fe
2+most of generation precipitated, and without Mg
2+precipitation, can obtain Mn(OH)
2and Fe(OH)
2precipitation, sediment separate after through thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add to add in the aqueous solution with solution in Mg
2+high-purity milk of lime of equivalent, regulating pH value is 8.0-12.0, makes the Mg in solution
2+be converted into completely
2and Mg(OH)
2precipitation, after Separation of Solid and Liquid, filter residue is produced refining liquid through slagging-off, preparation Mg(OH adds water)
2breast, passes into CO
2, generate the magnesium bicarbonate of solubilised state and the impurity of precipitation, press filtration removal of impurities.
Filtrate is reacted with ammoniacal liquor, generate magnesium hydroxide and carbonic hydroammonium, after isolated by filtration, magnesium hydroxide is through hydrothermal treatment consists, magnesium hydroxide crystal growth, prepare flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packaging again, carbonic hydroammonium decomposes ammonification, carbon dioxide and water and can be recycled.
Continue to add and Ca in chloride solution
2+the Na of equivalent
2cO
3, after cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packaging
3, the aqueous solution of NaCl and KCl evaporates through solvent, removes after water, extracts NaCl and KCl.By waste fused salt, cooling and muriatic heat of solution provides the required part heat of heating chloride solution.
Embodiment six: as shown in processing technological process Fig. 6 of waste fused salt, waste fused salt is direct cool to room temperature after coming out of the stove, then by waste fused salt layering fragmentation.Bottom is oxide skin(coating), is oxide and partial oxidation thing, and the main component of oxide is Al
2o
3, SiO
2, Fe
2o
3, TiO
2, CaO, MgO, account for the 13.0-15.0% of fused salt gross weight, in oxide skin(coating), contain the chloride of 10.3-30.5%; Top is coke layer; Middle part is chloride layer.To in oxide skin(coating), add industrial wastewater, make muriatic solution, after filtration, isolate solid phase and muriatic solution; In coke layer, add industrial wastewater, isolate coke and chloride solution, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
In chloride layer, add and account for chloride quality 45.0-90.0% water, formation temperature is the chloride supersaturated solution of 40-95 DEG C, isolates NaCl solid and hot chloride saturated solution after filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; By chloride saturated solution, add lime milk solution, then regulate pH=7.0-7.8, make the Mn of chloride solution
2+and Fe
2+most of generation precipitated, and without Mg
2+precipitation, can obtain Mn(OH)
2and Fe(OH)
2precipitation, sediment separate after through thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add to add in the aqueous solution with solution in Mg
2+high-purity milk of lime of equivalent, regulating pH value is 8.0-12.0, makes the Mg in solution
2+be converted into completely
2and Mg(OH)
2precipitation, after Separation of Solid and Liquid, filter residue is produced refining liquid through slagging-off, preparation Mg(OH adds water)
2breast, passes into CO
2, generate the magnesium bicarbonate of solubilised state and the impurity of precipitation, press filtration removal of impurities.
Filtrate is reacted with ammoniacal liquor, generate magnesium hydroxide and carbonic hydroammonium, after isolated by filtration, magnesium hydroxide is prepared flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packaging, and carbonic hydroammonium decomposes ammonification, carbon dioxide and water and can be recycled.
The CaCl2 that now contains high concentration in muriatic solution, and the temperature of solution higher (approximately 35-70 DEG C), now adopt cooling to process, and makes solution cool to room temperature, has a large amount of CaCl
22H
2o separates out, and obtains CaCl after Separation of Solid and Liquid
22H
2o, continues to add and Ca in chloride solution
2+the Na of equivalent
2cO
3, after cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packaging
3, the aqueous solution of NaCl and KCl evaporates through solvent, removes after water, extracts NaCl and KCl.By waste fused salt, cooling and muriatic heat of solution provides the required part heat of heating chloride solution.
Embodiment seven: as shown in processing technological process Fig. 7 of waste fused salt, waste fused salt is direct cool to room temperature after coming out of the stove, then by waste fused salt layering fragmentation.Bottom is oxide skin(coating), is oxide and partial oxidation thing, and the main component of oxide is Al
2o
3, SiO
2, Fe
2o
3, TiO
2, CaO, MgO, account for the 13.0-15.0% of fused salt gross weight, in oxide skin(coating), contain the chloride of 10.3-30.5%; Top is coke layer; Middle part is chloride layer.To in oxide skin(coating), add industrial wastewater, make muriatic solution, after filtration, isolate solid phase and muriatic solution; In coke layer, add industrial wastewater, isolate coke and chloride solution, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
In chloride layer, add and account for chloride quality 45.0-90.0% water, formation temperature is the chloride supersaturated solution of 40-95 DEG C, isolates NaCl solid and hot chloride saturated solution after filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; By chloride saturated solution, add lime milk solution, then regulate pH=7.0-7.8, make the Mn of chloride solution
2+and Fe
2+most of generation precipitated, and without Mg
2+precipitation, can obtain Mn(OH)
2and Fe(OH)
2precipitation, sediment separate after through thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add to add in the aqueous solution with solution in Mg
2+high-purity milk of lime of equivalent, regulating pH value is 8.0-12.0, makes the Mg in solution
2+be converted into completely
2and Mg(OH)
2precipitation, after Separation of Solid and Liquid, filter residue is produced refining liquid through slagging-off, preparation Mg(OH adds water)
2breast, passes into CO
2, generate the magnesium bicarbonate of solubilised state and the impurity of precipitation, press filtration removal of impurities.
Filtrate is reacted with ammoniacal liquor, generate magnesium hydroxide and carbonic hydroammonium, after isolated by filtration, magnesium hydroxide crystal growth, prepare flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packaging again, carbonic hydroammonium decomposes ammonification, carbon dioxide and water and can be recycled.
Muriatic solution is carried out to concentrate drying, produce a large amount of CaCl
22H
2o separates out, and obtains CaCl after Separation of Solid and Liquid
22H
2o, continues to add and Ca in chloride solution
2+the Na of equivalent
2cO
3, after cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packaging
3, the aqueous solution of NaCl and KCl evaporates through solvent, removes after water, extracts NaCl and KCl.By waste fused salt, cooling and muriatic heat of solution provides the required part heat of heating chloride solution.
Embodiment eight: as shown in processing technological process Fig. 8 of waste fused salt, waste fused salt is direct cool to room temperature after coming out of the stove, then by waste fused salt layering fragmentation.Bottom is oxide skin(coating), is oxide and partial oxidation thing, and the main component of oxide is Al
2o
3, SiO
2, Fe
2o
3, TiO
2, CaO, MgO, account for the 13.0-15.0% of fused salt gross weight, in oxide skin(coating), contain the chloride of 10.3-30.5%; Top is coke layer; Middle part is chloride layer.To in oxide skin(coating), add industrial wastewater, make muriatic solution, after filtration, isolate solid phase and muriatic solution; In coke layer, add industrial wastewater, isolate coke and chloride solution, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
In chloride layer, add and account for chloride quality 45.0-90.0% water, formation temperature is the chloride supersaturated solution of 40-95 DEG C, isolates NaCl solid and hot chloride saturated solution after filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; By chloride saturated solution, add lime milk solution, then regulate pH=7.0-7.8, make the Mn of chloride solution
2+and Fe
2+most of generation precipitated, and without Mg
2+precipitation, can obtain Mn(OH)
2and Fe(OH)
2precipitation, sediment separate after through thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add to add in the aqueous solution with solution in Mg
2+high-purity milk of lime of equivalent, regulating pH value is 8.0-12.0, makes the Mg in solution
2+be converted into completely
2and Mg(OH)
2precipitation, after Separation of Solid and Liquid, filter residue is produced refining liquid through slagging-off, preparation Mg(OH adds water)
2breast, passes into CO
2, generate the magnesium bicarbonate of solubilised state and the impurity of precipitation, press filtration removal of impurities.
Filtrate is reacted with ammoniacal liquor, generate magnesium hydroxide and carbonic hydroammonium, after isolated by filtration, magnesium hydroxide crystal growth, prepare flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packaging again, carbonic hydroammonium decomposes ammonification, carbon dioxide and water and can be recycled.
Muriatic solution is carried out to concentrate drying, produce a large amount of CaCl
22H
2o separates out, and obtains CaCl after Separation of Solid and Liquid
22H
2o, continues to add and Ca in chloride solution
2+the Na of equivalent
2cO
3, after cold filtration, solid phase obtains CaCO
3, calcine and generate quick lime, add water and digest and remove after impurity, logical people's carbon dioxide carries out carbonization, finally the slurries after carbonization is filtered, is dried and modification obtains nano-calcium carbonate calcium product.The aqueous solution of NaCl and KCl evaporates through solvent, removes after water, extracts NaCl and KCl.By waste fused salt, cooling and muriatic heat of solution provides the required part heat of heating chloride solution.
Claims (8)
1. a process for producing TiCl
4the method of the chlorination waste fused salt producing in process, described method comprises following process: produce TiCl
4the waste fused salt producing come out of the stove cooling after, by its layering fragmentation, chlorination waste fused salt, through water-soluble processing, is prepared into the supersaturated solution that is rich in NaCl, separate after slag and the aqueous solution, slag and the chloride that is dissolved in water are processed respectively, tentatively carried out deironing, demanganization, dechromisation, after filtration, obtain residue and supernatant, then supernatant is carried out to smart removal of impurities, filtration residue then adds alkali lye in supernatant, isolates sediment and washing removal Cl
-after, obtain magnesium goods and supernatant, magnesium goods are processed, prepare flame retardant of magnesium hydroxide or light magnesium oxide, in backward supernatant, add sodium carbonate, obtain the NaCl solution that calcium carbonate fine powder and purity are higher, then, respectively to calcium carbonate fine powder and NaCl solution-treated, realize the comprehensive utilization of waste fused salt.
2. a kind of process for producing TiCl according to claim 1
4the method of the chlorination waste fused salt producing in process, is characterized in that, chlorination waste fused salt is through water-soluble processing, be prepared into the supersaturated solution that is rich in NaCl, separate after slag and the aqueous solution, add NaOH to process slag, neutralization is that 7 rear press filtrations are dried to pH, obtains thick NaCl.
3. a kind of process for producing TiCl according to claim 1
4the method of the chlorination waste fused salt producing in process, is characterized in that, the chloride that is dissolved in water is added to OH
-carry out deironing, demanganization and dechromisation processing, introduce OH
-mode be NaOH, milk of lime and combination thereof.
4. a kind of process for producing TiCl according to claim 1
4the method of the chlorination waste fused salt producing in process, it is characterized in that, in removal supernatant, Mn, the Fe of remnants, the mode of Cr ion are in supernatant, to add reducing agent sodium hydrosulfite, make to be dissolved in Mn, Fe, Cr ion in solution, thoroughly remove with the form of metal M n, Fe, Cr; Or add the mode of oxidant by Fe
2+, Mn
2+be oxidized to Fe
3+and Mn
3+, make it generate Fe(OH)
3and Mn(OH)
3precipitation is removed, and the oxidant adding has H
20
2or air, then add Fe powder or reducing agent sodium hydrosulfite to remove the chromium in solution; Or directly add the Cr VI in iron powder, sodium hydrosulfite reducing solution, then use complexing agent ethylenediamine tetra-acetic acid (EDTA) and the removal of impurity of reducing agent sodium hydrosulfite.
5. a kind of process for producing TiCl according to claim 1
4the method of the chlorination waste fused salt producing in process, it is characterized in that the magnesium hydroxide being settled out, with after complexing agent ethylenediamine tetra-acetic acid (EDTA) and the removal of impurity of reducing agent sodium hydrosulfite, filtrate adds ammoniacal liquor to carry out aminating reaction, generate magnesium hydroxide, magnesium hydroxide, through surface treatment, is produced fire retardant magnesium hydroxide.
6. a kind of process for producing TiCl according to claim 1
4the method of the chlorination waste fused salt producing in process, is characterized in that, by the sediment of magnesium hydroxide and calcium hydroxide, then passes into CO
2, obtain heavy magnesium water Mg(HCO
3)
2filtrate, the filtrate of heavy magnesium water adds ammoniacal liquor to carry out aminating reaction, generates magnesium hydroxide, then through calcining to obtain activated magnesia.
7. a kind of process for producing TiCl according to claim 1
4the method of the chlorination waste fused salt producing in process, is characterized in that, is rich in the magnesium hydroxide of impurity, filters after cleaning, then uses complexing agent ethylenediamine tetra-acetic acid (EDTA) and the removal of impurity of reducing agent sodium hydrosulfite, and filter residue is passed into CO
2gas carries out carburizing reagent, add crystal control agent, coating material and dispersant simultaneously, generate magnesium bicarbonate and the lime deposit of solubilised state, through press filtration, filter cake is for containing magnesium calcium carbonate, and filtrate can be produced fire retardant magnesium hydroxide, basic magnesium carbonate and magnesia.
8. a kind of process for producing TiCl according to claim 1
4the method of the chlorination waste fused salt producing in process, in supernatant, add sodium carbonate, the calcium carbonate fine powder obtaining, can directly prepare calcium carbonate fine powder to calcium carbonate fine powder washing removal of impurities, or calcium carbonate fine powder calcining is generated to quick lime, add water and digest and remove after impurity, logical people's carbon dioxide carries out carbonization, finally the slurries after carbonization is filtered, dry and modification obtain nano-calcium carbonate calcium product.
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| CN103566719B (en) * | 2013-10-28 | 2016-04-06 | 沈阳化工大学 | Utilize and produce TiCl 4the waste chlorination molten salt produced prepares the method for desulfurizing agent raw material |
| CN104772317A (en) * | 2014-01-14 | 2015-07-15 | 贵阳铝镁设计研究院有限公司 | Comprehensive treatment method for waste fused salts and dust collection slag produced through titanium tetrachloride fused salt chlorination |
| CN103896308B (en) * | 2014-03-06 | 2016-01-20 | 沈阳化工大学 | A kind of process is containing the method for NaCl waste water |
| CN104198654B (en) * | 2014-08-15 | 2015-09-16 | 攀钢集团攀枝花钢铁研究院有限公司 | Fused salt chlorimation method produces the decision method of molten salt composition in titanium tetrachloride process |
| CN105861767B (en) * | 2016-04-05 | 2018-03-06 | 攀钢集团攀枝花钢铁研究院有限公司 | The method and its device of quick dissolving fused salt chlorimation slag |
| CN111908511B (en) * | 2019-05-16 | 2021-10-01 | 清华大学 | Method for removing calcium and magnesium ions in production of high-purity manganese sulfate |
| CN112010454A (en) * | 2019-05-30 | 2020-12-01 | 上海顺樊环保科技有限公司 | Electroplating nickel-containing wastewater treatment and recovery method |
| CN110668476A (en) * | 2019-10-10 | 2020-01-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing magnesia by utilizing fused salt chlorination slag |
| CN112299448A (en) * | 2020-11-20 | 2021-02-02 | 河南佰利联新材料有限公司 | Method for recovering sodium chloride from titanium white molten salt slag by chlorination process |
| CN112520777A (en) * | 2020-12-03 | 2021-03-19 | 山东鲁北企业集团总公司 | Process for preparing calcium chloride by using byproduct hydrochloric acid slag water of titanium white |
| CN113336244A (en) * | 2021-06-30 | 2021-09-03 | 攀钢集团研究院有限公司 | Method for removing ammonium from brine prepared from waste chlorination residues for ionic membrane caustic soda |
| CN113666390A (en) * | 2021-08-31 | 2021-11-19 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing ionic membrane caustic soda raw material brine by using fused salt chlorination residues |
| CN113582224B (en) * | 2021-09-06 | 2023-04-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Resource utilization method for titanium white waste acid leaching fused salt chlorination slag |
| CN118637905A (en) * | 2021-12-28 | 2024-09-13 | 元颉新材料科技(浙江)有限公司 | Pure crystal phase high-quality factor nano-sized magnesium calcium titanate ceramic powder and preparation method thereof |
| CN115818677A (en) * | 2022-12-07 | 2023-03-21 | 攀钢集团研究院有限公司 | Preparation method of magnesium hydroxide |
| CN115849416A (en) * | 2022-12-28 | 2023-03-28 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity basic magnesium carbonate from fused salt chlorination residues |
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| CN102718233B (en) * | 2011-12-15 | 2014-04-30 | 沈阳化工大学 | Method for combined treatment on chlorinated waste molten salts and Cl-containing waste water |
| CN102443710B (en) * | 2011-12-15 | 2013-08-28 | 沈阳化工大学 | Method for treating scrapped molten salt generated in molten salt chlorination production method of TiCl4 |
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