CN103011203A - 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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- CN103011203A CN103011203A CN2012105217326A CN201210521732A CN103011203A CN 103011203 A CN103011203 A CN 103011203A CN 2012105217326 A CN2012105217326 A CN 2012105217326A CN 201210521732 A CN201210521732 A CN 201210521732A CN 103011203 A CN103011203 A CN 103011203A
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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 that produces in the process.
Background technology
The standby TiCl of fused salt chlorimation legal system
4Maximum advantage is to the wide accommodation of raw material, suitable treatment high calcium magnesium titanium slag and TiO
2The titanium slag that grade is lower, quality product is excellent, the TiCl of production
4Account for about 40% of present World Titanium industry consumption.The schreyerite of the Flos Bombacis Malabarici-Xichang Region 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 and titanium dioxide, in the fused salt chlorimation production process, can produce a large amount of fused salt waste residues, abraum salt waste residue main component is muriate, as deal with improperly, the hydrolysis of generation chloride-sublimation, to cause the deterioration of waters, edatope on every side, cause simultaneously the loss waste of wherein measuring useful resources.Abroad with after the water-soluble filtration of chloride slag, gained filtrate is annotated people 1600m with sub-surface by special underground filling system, although be perfused with the suitable degree of depth, yet in case geological movement occurs, may polluted underground water system even cause the pollution of surface environment.External other, the landfill that the fused salt waste residue has enters the abandoned mine well, the employing that has with lime yard every lay in the wasteland, domestic is to take lime to stir neutralizing treatment to stack the slag field again, all there is potential pollution in these methods, such as polluted underground water, salinization soil etc., do not tackle the problem at its root.
Magnesium hydroxide belongs to the addition type inorganic combustion inhibitor, compare with similar inorganic combustion inhibitor, macromolecular material is obtained outside the good flame retardant effect, can also suppress the generation of the poisonous gass such as smog and hydrogen halide, has better smoke suppressing effect, be magnesium hydroxide remove have fire-retardant, eliminate smoke and fill triple functions, give simultaneously material non-toxic, non-corrosiveness.Magnesium hydroxide is all unharmful substance dischargings 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 having resistance to acid, the acidity and the corrosive gases that produce with combustion processes in the energy are a kind of environmentally friendly Green Flammability agent.
Nano-calcium carbonate can be used as a kind of functional filler and is applied in widely the fields such as plastics, rubber, papermaking, seal gum after surface modification.
China is that the big producing country of in the world calcium carbonate product also is consumption big country, and now annual production 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 and modified calcium carbonate product that they produce all are in world lead level; The U.S. biases toward production papermaking and coating calcium carbonate product: Britain is partial to study the calcium carbonate that adds in the used plastics of automobile making, and Germany biases toward the research that filler is used 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 that produces in the process.The present invention utilizes the chlorination waste fused salt to be raw material, reclaims the raw materials such as coke, sodium-chlor, and preparation CaCO
3Micro mist and flame retardant of magnesium hydroxide are realized the comprehensive utilization of waste fused salt, solve long-term puzzlement fused salt electrolysis process and prepare TiCl
4The waste fused salt that exists and contain Cl
-The problem of contaminated wastewater environment.
The objective 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 that produces in the process, described method comprises following process: produce TiCl
4The waste fused salt that produces is come out of the stove after the cooling, its layering is broken, and the chlorination waste fused salt is prepared into the supersaturated solution that is rich in NaCl through water-soluble processing, after separating slag and the aqueous solution, slag and the muriate that is dissolved in water are processed respectively, tentatively carried out deironing, demanganization, dechromisation, obtain residue and supernatant liquor after the filtration, then supernatant liquor is carried out smart removal of impurities, then filtration residue adds alkali lye in supernatant liquor, isolate throw out and washing removal Cl
-After, obtain magnesium goods and supernatant liquor, the magnesium goods are processed, preparation flame retardant of magnesium hydroxide and light magnesium oxide, add yellow soda ash in the backward supernatant liquor, obtain the higher NaCl solution of calcium carbonate fine powder and purity, then respectively to calcium carbonate fine powder and the NaCl solution-treated, namely realize the comprehensive utilization of waste fused salt.
Described a kind of process for producing TiCl
4The method of the chlorination waste fused salt that produces in the process, the chlorination waste fused salt is prepared into the supersaturated solution that is rich in NaCl through water-soluble processing, behind separation slag and the aqueous solution, slag is added NaOH process, and neutralization is 7 rear press filtrations oven dry to pH, obtains thick NaCl.
Described a kind of process for producing TiCl
4The method of the chlorination waste fused salt that produces in the process adds OH with the muriate that is dissolved in water
-Carry out deironing, demanganization and dechromisation and process, 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 that produces in the process, the mode of removing Mn, Fe remaining in the supernatant liquor, Cr ion are to add the reductive agent vat powder in supernatant liquor, make Mn, the Fe, the Cr ion that are dissolved in the solution, thoroughly remove with the form of metal M n, Fe, Cr; Or the mode of adding oxygenant is with 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 oxygenant of adding has H
20
2Or air, then add the chromium in Fe powder or the reductive agent vat powder removal solution; Or directly add sexavalent chrome in iron powder, the vat powder reducing solution, then use complexing agent ethylenediamine tetraacetic acid (EDTA) (EDTA) and the removal of impurity of reductive agent vat powder.
Described a kind of process for producing TiCl
4The method of the chlorination waste fused salt that produces in the process adds NaOH solution in supernatant liquor, be settled out magnesium hydroxide.With the magnesium hydroxide that is settled out, after complexing agent ethylenediamine tetraacetic acid (EDTA) (EDTA) and the removal of impurity of reductive agent vat powder, filtrate adds ammoniacal liquor and carries out aminating reaction, produces fire retardant magnesium hydroxide.
Described a kind of process for producing TiCl
4The method of the chlorination waste fused salt that produces in the process, or in supernatant liquor, add milk of lime, with the throw out 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 add ammoniacal liquor and carry out aminating reaction, the preparation magnesium hydroxide.
Described a kind of process for producing TiCl
4The method of the chlorination waste fused salt that produces in the process is rich in the magnesium hydroxide of impurity, filter clean after, then use complexing agent ethylenediamine tetraacetic acid (EDTA) (EDTA) and the removal of impurity of reductive agent vat powder, filter residue is passed into CO
2Gas carries out carburizing reagent, add simultaneously crystal control agent, coating materials and dispersion agent, generate Magnesium hydrogen carbonate 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, magnesium basic carbonate and magnesium oxide.
Described a kind of process for producing TiCl
4The method of the chlorination waste fused salt that produces in the process adds yellow soda ash in the supernatant liquor, the calcium carbonate fine powder that obtains can directly prepare calcium carbonate fine powder to calcium carbonate fine powder washing removal of impurities.Or with calcium carbonate fine powder calcining generation unslaked lime, after adding water digestion and removing impurity, logical people's carbonic acid gas carries out carbonization, at last the dope filtration after the carbonization, drying and modification is namely got the nano-calcium carbonate calcium product.
Advantage of the present invention and effect are:
The present invention can solve the standby TiCl of long-term puzzlement fused salt chlorimation legal system
4The difficult problem that the waste fused salt that exists is processed, recyclable sodium-chlor, 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 magnesium basic carbonate and magnesium oxide).
Description of drawings
Fig. 1 is for processing the technical process embodiment 1 of waste fused salt;
Fig. 2 is for processing the technical process embodiment 2 of waste fused salt;
Fig. 3 is for processing the technical process embodiment 3 of waste fused salt;
Fig. 4 is for processing the technical process embodiment 4 of waste fused salt;
Fig. 5 is for processing the technical process embodiment 5 of waste fused salt;
Fig. 6 is for processing the technical process embodiment 6 of waste fused salt;
Fig. 7 is for processing the technical process embodiment 7 of waste fused salt;
Fig. 8 is for processing the technical process embodiment 8 of waste fused salt.
Embodiment
The present invention is described in detail below in conjunction with the accompanying drawing illustrated embodiment.
Embodiment one: shown in the technical process Fig. 1 that processes waste fused salt, and the waste fused salt rear direct cool to room temperature of coming out of the stove, then that the waste fused salt layering is broken.The bottom is oxide skin, is oxide compound and partial oxidation thing, and the main component of oxide compound 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, contain the muriate of 10.3-30.5% in the oxide skin; Top is coke layer; The middle part is chloride layer.To add trade effluent in the oxide skin, make muriatic solution, isolate solid phase and muriatic solution after the filtration; Add trade effluent in the coke layer, isolate coke and chloride soln, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
Add in the chloride layer and account for muriate quality 45.0-90.0% water, formation temperature is 40-95 ℃ muriate supersaturated solution, isolate the muriate saturated solution of NaCl solid and heat after the filtration, isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight, isolated NaCl is added NaOH neutralize after pH equals 7, can return the molten salt furnace reuse after the oven dry; Then with the muriate saturated solution, at first add NaOH, adjust to pH=5.2, be precipitated thing and chloride soln, throw out 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 soln
2+And Fe
2+The most of generation precipitated, and without Mg
2+Precipitation passes into air afterwards, makes the Mn that remains in the chloride soln
2+And Fe
2+Be converted into Fe
3+And Mn
3+Thereby, be converted into Fe(OH)
3And Mn(OH)
3Then Precipitation adds reducing powder, and the heavy metal ion conversion atoms metal in the chloride soln is separated out, and the metal ions such as the Fe in the chloride soln, Mn, Cr are removed substantially fully like this, Mn(OH)
2And Fe(OH)
2Content be 28.3%-31.5%, remaining is compound and impurity in the iron content, throw out separates by thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add add in the aqueous solution with solution in Mg
2+And Ca
2+The NaOH of equivalent makes the Ca in the solution
2+And Mg
2+Be converted into Ca(OH fully)
2And Mg(OH)
2Precipitation, after the solid-liquid separation, filter residue is produced refining liquid through slagging-off, adds water preparation dolomite ash breast, passes into CO
2Adding the 0.1-0.6% sodium polyacrylate that accounts for magnesium calcium carbonate dry basic weight is dispersion agent, add the 0.1-0.6% polyoxyethylene glycol account for magnesium calcium carbonate dry basic weight-be modifier, take aluminum trichloride (anhydrous) (AlCl3) and ethylenediamine tetraacetic acid (EDTA) (EDTA) as crystal control agent and dispersion agent, generate the Magnesium hydrogen carbonate of solubilised state and the calcium carbonate of precipitation, through press filtration, filter cake is produced the ultra-fine magnesium calcium carbonate product that contains for containing magnesium calcium carbonate through surface modification, drying, classification, packing.
Filtrate and ammoniacal liquor react, generate magnesium hydroxide and bicarbonate of ammonia, after the filtering separation, magnesium hydroxide prepares flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packing again, and bicarbonate of ammonia decomposes ammonification, carbonic acid gas and water and can be recycled.
Continuation adds and Ca in chloride soln
2+The Na of equivalent
2CO
3, behind cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packing
3
The aqueous solution of part NaCl is sent into chlor-alkali plant as the raw material of chemical industry for making chlorine and alkali through processing.The aqueous solution of part NaCl and KCl behind the removal water, extracts NaCl and KCl through solvent evaporation.The required part heat of heating chloride soln is provided by waste fused salt cooling and muriatic solution heat.
Embodiment two: shown in the technical process Fig. 2 that processes waste fused salt, and the waste fused salt rear direct cool to room temperature of coming out of the stove, then that the waste fused salt layering is broken.The bottom is oxide skin, is oxide compound and partial oxidation thing, and the main component of oxide compound 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, contain the muriate of 10.3-30.5% in the oxide skin; Top is coke layer; The middle part is chloride layer.To add trade effluent in the oxide skin, make muriatic solution, isolate solid phase and muriatic solution after the filtration; Add trade effluent in the coke layer, isolate coke and chloride soln, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
Adding accounts for muriate quality 45.0-90.0% water in the chloride layer, and formation temperature is 40-95 ℃ muriate supersaturated solution, isolates the muriate saturated solution of NaCl solid and heat after the filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; With the muriate saturated solution, at first add milk of lime, adjust to pH=5.2, be precipitated thing and chloride soln, throw out is mainly Fe(OH)
3, after cleaning calcining, prepare ferric oxide, then add milk of lime, regulate pH=6.0, make the Mn of chloride soln
2+And Fe
2+The most of generation precipitated, and Mg
2+Precipitation does not pass into hydrogen peroxide afterwards, makes the Mn that remains in the chloride soln
2+And Fe
2+Be converted into Fe
3+And Mn
3+Thereby, be converted into Fe(OH)
3And Mn(OH)
3Then Precipitation adds reducing powder, and the heavy metal ion conversion atoms metal in the chloride soln is separated out, and the metal ions such as the Fe in the chloride soln, Mn, Cr are removed substantially fully like this, Mn(OH)
2And Fe(OH)
2Content be 28.3%-31.5%, remaining is compound and the impurity such as iron content, throw out separate by clean, thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continuation add in the aqueous solution with solution in Mg
2+The fat lime breast of equivalent makes the Mg in the solution
2+Be converted into Mg(OH fully)
2Precipitation, simultaneously Mg(OH)
2Precipitation also is mixed with a small amount of Ca(OH)
2, after the solid-liquid separation, filter residue is produced refining liquid through slagging-off, adds water again and generates dolomite ash breast, then CO
2Carry out carburizing reagent, generate Magnesium hydrogen carbonate and contain magnesium calcium carbonate, after calcium carbonate is removed in press filtration, mother liquor obtains magnesium basic carbonate through pyrolysis, again after filtration, drying obtains the hydration magnesium basic carbonate, the calcium carbonate filter cake drying obtains containing magnesium calcium carbonate, the wet magnesium basic carbonate that pyrolysis obtains after filtering, and the drying calcining obtains industrial magnesium oxide again.
Continuation adds and Ca in chloride soln
2+The Na of equivalent
2CO
3Octadecanol phosphoric acid ester (ODP) dispersion agent, Sodium hexametaphosphate 99 is controlled at 1%～3% (the crystal-directing-agent consumption accounts for the massfraction of calcium carbonate solid amount) as the general consumption of crystalline form directed agents and selects the crystal-directing-agent Sodium hexametaphosphate 99, and behind cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packing
3,
Embodiment three: shown in the technical process Fig. 3 that processes waste fused salt, and the waste fused salt rear direct cool to room temperature of coming out of the stove, then that the waste fused salt layering is broken.The bottom is oxide skin, is oxide compound and partial oxidation thing, and the main component of oxide compound 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, contain the muriate of 10.3-30.5% in the oxide skin; Top is coke layer; The middle part is chloride layer.To add trade effluent in the oxide skin, make muriatic solution, isolate solid phase and muriatic solution after the filtration; Add trade effluent in the coke layer, isolate coke and chloride soln, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
Adding accounts for muriate quality 45.0-90.0% water in the chloride layer, and formation temperature is 40-95 ℃ muriate supersaturated solution, isolates the muriate saturated solution of NaCl solid and heat after the filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; With the muriate saturated solution, at first add milk of lime, adjust to pH=5.2, be precipitated thing and chloride soln, throw out 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 soln
2+And Fe
2+The most of generation precipitated, and without Mg
2+Precipitation passes into air afterwards, makes the Mn that remains in the chloride soln
2+And Fe
2+Be converted into Fe
3+And Mn
3+Thereby, be converted into Fe(OH)
3And Mn(OH)
3Then Precipitation adds reducing powder, and the heavy metal ion conversion atoms metal in the chloride soln is separated out, and the metal ions such as the Fe in the chloride soln, Mn, Cr are removed substantially fully like this, Mn(OH)
2And Fe(OH)
2Content be 28.3%-31.5%, remaining is compound and impurity in the iron content, throw out separates by thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add add in the aqueous solution with solution in Mg
2+And Ca
2+The ammoniacal liquor of equivalent makes the Ca in the solution
2+And Mg
2+Be converted into Ca(OH fully)
2And Mg(OH)
2Precipitation, after the solid-liquid separation, filter residue is produced refining liquid through slagging-off, adds water preparation dolomite ash breast, passes into CO
2Adding the 0.1-0.6% sodium polyacrylate that accounts for magnesium calcium carbonate dry basic weight is dispersion agent, add 0.1-0.6% polyoxyethylene glycol one phosphoric acid that accounts for magnesium calcium carbonate dry basic weight and extremely be modifier, take aluminum trichloride (anhydrous) (AlCl3) and ethylenediamine tetraacetic acid (EDTA) (EDTA) as crystal control agent and dispersion agent, generate the Magnesium hydrogen carbonate of solubilised state and the calcium carbonate of precipitation, through press filtration, filter cake is produced the ultra-fine magnesium calcium carbonate product that contains for containing magnesium calcium carbonate through surface modification, drying, classification, packing.
Filtrate and ammoniacal liquor react, generate magnesium hydroxide and bicarbonate of ammonia, after the filtering separation, magnesium hydroxide is through hydrothermal treatment consists, the magnesium hydroxide crystal growth, prepare flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packing again, bicarbonate of ammonia decomposes ammonification, carbonic acid gas and water and can be recycled.
Continuation adds and Ca in chloride soln
2+The Na of equivalent
2CO
3, behind cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packing
3, solution prepares Na by the Hou Shi alkali-making process after treatment
2CO
3And NH
4Cl.
Embodiment four: shown in the technical process Fig. 4 that processes waste fused salt, and the waste fused salt rear direct cool to room temperature of coming out of the stove, then that the waste fused salt layering is broken.The bottom is oxide skin, is oxide compound and partial oxidation thing, and the main component of oxide compound 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, contain the muriate of 10.3-30.5% in the oxide skin; Top is coke layer; The middle part is chloride layer.To add trade effluent in the oxide skin, make muriatic solution, isolate solid phase and muriatic solution after the filtration; Add trade effluent in the coke layer, isolate coke and chloride soln, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
Adding accounts for muriate quality 45.0-90.0% water in the chloride layer, and formation temperature is 40-95 ℃ muriate supersaturated solution, isolates the muriate saturated solution of NaCl solid and heat after the filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; With the muriate saturated solution, at first add milk of lime, adjust to pH=5.2, be precipitated thing and chloride soln, throw out 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 soln
2+And Fe
2+The most of generation precipitated, and without Mg
2+Precipitation passes into air afterwards, makes the Mn that remains in the chloride soln
2+And Fe
2+Be converted into Fe
3+And Mn
3+Thereby, be converted into Fe(OH)
3And Mn(OH)
3Then Precipitation adds reducing powder, and the heavy metal ion conversion atoms metal in the chloride soln is separated out, and the metal ions such as the Fe in the chloride soln, Mn, Cr are removed substantially fully like this, Mn(OH)
2And Fe(OH)
2Content be 28.3%-31.5%, remaining is compound and impurity in the iron content, throw out separates by thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add add in the aqueous solution with solution in Mg
2+The high-quality Ca(OH of equivalent)
2, make the Mg in the solution
2+Be converted into Mg(OH fully)
2Precipitation, simultaneously Mg(OH)
2Precipitation also is mixed with a small amount of Ca(OH)
2, after the solid-liquid separation, filter residue is produced refining liquid through slagging-off, adds water again and generates dolomite ash breast, then CO
2Carry out carburizing reagent, generate Magnesium hydrogen carbonate and contain magnesium calcium carbonate, after calcium carbonate is removed in press filtration, filtrate and ammoniacal liquor react, generate magnesium hydroxide and bicarbonate of ammonia, after the filtering separation, magnesium hydroxide prepares flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packing again, and bicarbonate of ammonia decomposes ammonification, carbonic acid gas and water and can be recycled.
Continuation adds and Ca in chloride soln
2+The Na of equivalent
2CO
3, behind cold filtration, solid phase obtains CaCO
3, all be that Wingdale is calcined generation unslaked lime, after adding water digestion and removing impurity, logical people's carbonic acid gas carries out carbonization, at last the dope filtration after the carbonization, drying and modification is namely got the nano-calcium carbonate calcium product.Solution prepares Na by the Hou Shi alkali-making process after treatment
2CO
3And NH
4Cl.
Embodiment five: shown in the technical process Fig. 5 that processes waste fused salt, and the waste fused salt rear direct cool to room temperature of coming out of the stove, then that the waste fused salt layering is broken.The bottom is oxide skin, is oxide compound and partial oxidation thing, and the main component of oxide compound 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, contain the muriate of 10.3-30.5% in the oxide skin; Top is coke layer; The middle part is chloride layer.To add trade effluent in the oxide skin, make muriatic solution, isolate solid phase and muriatic solution after the filtration; Add trade effluent in the coke layer, isolate coke and chloride soln, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
Adding accounts for muriate quality 45.0-90.0% water in the chloride layer, and formation temperature is 40-95 ℃ muriate supersaturated solution, isolates the muriate saturated solution of NaCl solid and heat after the filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; With the muriate saturated solution, add lime milk solution, then regulate pH=7.0-7.8, make the Mn of chloride soln
2+And Fe
2+The most of generation precipitated, and without Mg
2+Precipitation can obtain Mn(OH)
2And Fe(OH)
2Precipitation, throw out separates by thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add add in the aqueous solution with solution in Mg
2+High-purity milk of lime of equivalent, regulating the pH value is 8.0-12.0, makes the Mg in the solution
2+Be converted into fully
2And Mg(OH)
2Precipitation, after the solid-liquid separation, filter residue is produced refining liquid through slagging-off, adds water preparation Mg(OH)
2Breast passes into CO
2, generate the Magnesium hydrogen carbonate of solubilised state and the impurity of precipitation, the press filtration removal of impurities.
Filtrate and ammoniacal liquor react, generate magnesium hydroxide and bicarbonate of ammonia, after the filtering separation, magnesium hydroxide is through hydrothermal treatment consists, the magnesium hydroxide crystal growth, prepare flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packing again, bicarbonate of ammonia decomposes ammonification, carbonic acid gas and water and can be recycled.
Continuation adds and Ca in chloride soln
2+The Na of equivalent
2CO
3, behind cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packing
3, the aqueous solution of NaCl and KCl behind the removal water, extracts NaCl and KCl through solvent evaporation.The required part heat of heating chloride soln is provided by waste fused salt cooling and muriatic solution heat.
Embodiment six: shown in the technical process Fig. 6 that processes waste fused salt, and the waste fused salt rear direct cool to room temperature of coming out of the stove, then that the waste fused salt layering is broken.The bottom is oxide skin, is oxide compound and partial oxidation thing, and the main component of oxide compound 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, contain the muriate of 10.3-30.5% in the oxide skin; Top is coke layer; The middle part is chloride layer.To add trade effluent in the oxide skin, make muriatic solution, isolate solid phase and muriatic solution after the filtration; Add trade effluent in the coke layer, isolate coke and chloride soln, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
Adding accounts for muriate quality 45.0-90.0% water in the chloride layer, and formation temperature is 40-95 ℃ muriate supersaturated solution, isolates the muriate saturated solution of NaCl solid and heat after the filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; With the muriate saturated solution, add lime milk solution, then regulate pH=7.0-7.8, make the Mn of chloride soln
2+And Fe
2+The most of generation precipitated, and without Mg
2+Precipitation can obtain Mn(OH)
2And Fe(OH)
2Precipitation, throw out separates by thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add add in the aqueous solution with solution in Mg
2+High-purity milk of lime of equivalent, regulating the pH value is 8.0-12.0, makes the Mg in the solution
2+Be converted into fully
2And Mg(OH)
2Precipitation, after the solid-liquid separation, filter residue is produced refining liquid through slagging-off, adds water preparation Mg(OH)
2Breast passes into CO
2, generate the Magnesium hydrogen carbonate of solubilised state and the impurity of precipitation, the press filtration removal of impurities.
Filtrate and ammoniacal liquor react, generate magnesium hydroxide and bicarbonate of ammonia, after the filtering separation, magnesium hydroxide prepares flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packing, and bicarbonate of ammonia decomposes ammonification, carbonic acid gas and water and can be recycled.
Contain the CaCl2 of high density this moment in the muriatic solution, and the temperature of solution higher (approximately 35-70 ℃), adopts this moment cooling to process, and makes the solution cool to room temperature, has a large amount of CaCl
22H
2O separates out, and obtains CaCl after the solid-liquid separation
22H
2O continues to add and Ca in chloride soln
2+The Na of equivalent
2CO
3, behind cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packing
3, the aqueous solution of NaCl and KCl behind the removal water, extracts NaCl and KCl through solvent evaporation.The required part heat of heating chloride soln is provided by waste fused salt cooling and muriatic solution heat.
Embodiment seven: shown in the technical process Fig. 7 that processes waste fused salt, and the waste fused salt rear direct cool to room temperature of coming out of the stove, then that the waste fused salt layering is broken.The bottom is oxide skin, is oxide compound and partial oxidation thing, and the main component of oxide compound 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, contain the muriate of 10.3-30.5% in the oxide skin; Top is coke layer; The middle part is chloride layer.To add trade effluent in the oxide skin, make muriatic solution, isolate solid phase and muriatic solution after the filtration; Add trade effluent in the coke layer, isolate coke and chloride soln, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
Adding accounts for muriate quality 45.0-90.0% water in the chloride layer, and formation temperature is 40-95 ℃ muriate supersaturated solution, isolates the muriate saturated solution of NaCl solid and heat after the filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; With the muriate saturated solution, add lime milk solution, then regulate pH=7.0-7.8, make the Mn of chloride soln
2+And Fe
2+The most of generation precipitated, and without Mg
2+Precipitation can obtain Mn(OH)
2And Fe(OH)
2Precipitation, throw out separates by thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add add in the aqueous solution with solution in Mg
2+High-purity milk of lime of equivalent, regulating the pH value is 8.0-12.0, makes the Mg in the solution
2+Be converted into fully
2And Mg(OH)
2Precipitation, after the solid-liquid separation, filter residue is produced refining liquid through slagging-off, adds water preparation Mg(OH)
2Breast passes into CO
2, generate the Magnesium hydrogen carbonate of solubilised state and the impurity of precipitation, the press filtration removal of impurities.
Filtrate and ammoniacal liquor react, generate magnesium hydroxide and bicarbonate of ammonia, after the filtering separation, the magnesium hydroxide crystal growth, prepare flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packing again, bicarbonate of ammonia decomposes ammonification, carbonic acid gas and water and can be recycled.
Muriatic solution is carried out concentrate drying, produce a large amount of CaCl
22H
2O separates out, and obtains CaCl after the solid-liquid separation
22H
2O continues to add and Ca in chloride soln
2+The Na of equivalent
2CO
3, behind cold filtration, solid phase obtains nanometer CaCO
3, prepare nanometer CaCO through washing, oven dry, classification, packing
3, the aqueous solution of NaCl and KCl behind the removal water, extracts NaCl and KCl through solvent evaporation.The required part heat of heating chloride soln is provided by waste fused salt cooling and muriatic solution heat.
?
Embodiment eight: shown in the technical process Fig. 8 that processes waste fused salt, and the waste fused salt rear direct cool to room temperature of coming out of the stove, then that the waste fused salt layering is broken.The bottom is oxide skin, is oxide compound and partial oxidation thing, and the main component of oxide compound 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, contain the muriate of 10.3-30.5% in the oxide skin; Top is coke layer; The middle part is chloride layer.To add trade effluent in the oxide skin, make muriatic solution, isolate solid phase and muriatic solution after the filtration; Add trade effluent in the coke layer, isolate coke and chloride soln, the content of coke accounts for the 13.0-16.0% of waste fused salt gross weight.
Adding accounts for muriate quality 45.0-90.0% water in the chloride layer, and formation temperature is 40-95 ℃ muriate supersaturated solution, isolates the muriate saturated solution of NaCl solid and heat after the filtration, and isolated NaCl accounts for the 23.0-28.0% of waste fused salt gross weight; With the muriate saturated solution, add lime milk solution, then regulate pH=7.0-7.8, make the Mn of chloride soln
2+And Fe
2+The most of generation precipitated, and without Mg
2+Precipitation can obtain Mn(OH)
2And Fe(OH)
2Precipitation, throw out separates by thermal dehydration, can be used as the raw material of ferromanganese smelting.
Continue to add add in the aqueous solution with solution in Mg
2+High-purity milk of lime of equivalent, regulating the pH value is 8.0-12.0, makes the Mg in the solution
2+Be converted into fully
2And Mg(OH)
2Precipitation, after the solid-liquid separation, filter residue is produced refining liquid through slagging-off, adds water preparation Mg(OH)
2Breast passes into CO
2, generate the Magnesium hydrogen carbonate of solubilised state and the impurity of precipitation, the press filtration removal of impurities.
Filtrate and ammoniacal liquor react, generate magnesium hydroxide and bicarbonate of ammonia, after the filtering separation, the magnesium hydroxide crystal growth, prepare flame retardant of magnesium hydroxide through surface treatment, filtration, washing, oven dry, classification, packing again, bicarbonate of ammonia decomposes ammonification, carbonic acid gas and water and can be recycled.
Muriatic solution is carried out concentrate drying, produce a large amount of CaCl
22H
2O separates out, and obtains CaCl after the solid-liquid separation
22H
2O continues to add and Ca in chloride soln
2+The Na of equivalent
2CO
3, behind the cold filtration, solid phase obtains CaCO
3, calcine generation unslaked lime, after adding water digestion and removing impurity, logical people's carbonic acid gas carries out carbonization, at last the dope filtration after the carbonization, drying and modification is namely got the nano-calcium carbonate calcium product.The aqueous solution of NaCl and KCl behind the removal water, extracts NaCl and KCl through solvent evaporation.The required part heat of heating chloride soln is provided by waste fused salt cooling and muriatic solution heat.
Claims (8)
1. process for producing TiCl
4The method of the chlorination waste fused salt that produces in the process, described method comprises following process: produce TiCl
4The waste fused salt that produces is come out of the stove after the cooling, its layering is broken, and the chlorination waste fused salt is prepared into the supersaturated solution that is rich in NaCl through water-soluble processing, after separating slag and the aqueous solution, slag and the muriate that is dissolved in water are processed respectively, tentatively carried out deironing, demanganization, dechromisation, obtain residue and supernatant liquor after the filtration, then supernatant liquor is carried out smart removal of impurities, then filtration residue adds alkali lye in supernatant liquor, isolate throw out and washing removal Cl
-After, obtain magnesium goods and supernatant liquor, the magnesium goods are processed, the preparation flame retardant of magnesium hydroxide or or light magnesium oxide, add yellow soda ash in the backward supernatant liquor, obtain the higher NaCl solution of calcium carbonate fine powder and purity, then respectively to calcium carbonate fine powder and the NaCl solution-treated, namely realize the comprehensive utilization of waste fused salt.
2. described a kind of process for producing TiCl according to claim 1
4The method of the chlorination waste fused salt that produces in the process is characterized in that, the chlorination waste fused salt is through water-soluble processing, be prepared into the supersaturated solution that is rich in NaCl, behind separation slag and the aqueous solution, slag added NaOH process, neutralization is 7 rear press filtration oven dry 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 that produces in the process is characterized in that, the muriate that is dissolved in water is added OH
-Carry out deironing, demanganization and dechromisation and process, 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 that produces in the process, it is characterized in that, the mode of removing Mn, Fe remaining in the supernatant liquor, Cr ion is to add the reductive agent vat powder in supernatant liquor, makes Mn, the Fe, the Cr ion that are dissolved in the solution, thoroughly removes with the form of metal M n, Fe, Cr; Or the mode of adding oxygenant is with 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 oxygenant of adding has H
20
2Or air, then add the chromium in Fe powder or the reductive agent vat powder removal solution; Or directly add sexavalent chrome in iron powder, the vat powder reducing solution, then use complexing agent ethylenediamine tetraacetic acid (EDTA) (EDTA) and the removal of impurity of reductive agent vat powder.
5. a kind of process for producing TiCl according to claim 1
4The method of the chlorination waste fused salt that produces in the process, it is characterized in that the magnesium hydroxide that to be settled out, after complexing agent ethylenediamine tetraacetic acid (EDTA) (EDTA) and the removal of impurity of reductive agent vat powder, filtrate adds ammoniacal liquor and carries out aminating reaction, generate magnesium hydroxide, magnesium hydroxide is produced fire retardant magnesium hydroxide through surface treatment.
6. a kind of process for producing TiCl according to claim 1
4The method of the chlorination waste fused salt that produces in the process is characterized in that, with the throw out 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 and carries out aminating reaction, generates magnesium hydroxide, again through calcining to get activated magnesia.
7. a kind of process for producing TiCl according to claim 1
4The method of the chlorination waste fused salt that produces in the process is characterized in that, is rich in the magnesium hydroxide of impurity, and then filtration uses complexing agent ethylenediamine tetraacetic acid (EDTA) (EDTA) and the removal of impurity of reductive agent vat powder after cleaning, and filter residue is passed into CO
2Gas carries out carburizing reagent, add simultaneously crystal control agent, coating materials and dispersion agent, generate Magnesium hydrogen carbonate 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, magnesium basic carbonate and magnesium oxide.
8. a kind of process for producing TiCl according to claim 1
4The method of the chlorination waste fused salt that produces in the process, add yellow soda ash in the supernatant liquor, the calcium carbonate fine powder that obtains, can directly prepare calcium carbonate fine powder to calcium carbonate fine powder washing removal of impurities, or with calcium carbonate fine powder calcining generation unslaked lime, after adding water digestion and removing impurity, logical people's carbonic acid gas carries out carbonization, at last the dope filtration after the carbonization, drying and modification is namely got the nano-calcium carbonate calcium product.
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