CN113816399A - Method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag - Google Patents
Method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag Download PDFInfo
- Publication number
- CN113816399A CN113816399A CN202111142929.4A CN202111142929A CN113816399A CN 113816399 A CN113816399 A CN 113816399A CN 202111142929 A CN202111142929 A CN 202111142929A CN 113816399 A CN113816399 A CN 113816399A
- Authority
- CN
- China
- Prior art keywords
- nacl
- recycling
- brine
- resources
- salt chlorination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 102
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 27
- 239000010936 titanium Substances 0.000 title claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002893 slag Substances 0.000 title claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 61
- 239000012267 brine Substances 0.000 claims abstract description 55
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002699 waste material Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 20
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000012716 precipitator Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 5
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 229920001429 chelating resin Polymers 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 238000007670 refining Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000002159 abnormal effect Effects 0.000 description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 5
- 239000001095 magnesium carbonate Substances 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910001427 strontium ion Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for recycling NaCl and recovering Fe, Mn and Mg resources in titanium slag together, and belongs to the technical field of titanium tetrachloride waste salt treatment and deep refining of chlor-alkali chemical salt water. The method comprises the following steps: a. leaching, b, preparing mixtureCombining brine, c, preparing magnesium-removed NaCl brine, d, preparing NaCl products, drying and recycling the NaCl products in a fused salt chlorination furnace, e, preparing primary brine saturated by caustic soda through an ionic membrane, f, deeply reducing and removing impurities, g, synergistically removing Mg2+、CO3 2‑、SO4 2‑Plasma, h, neutralization, filtration and impurity removal, and i, deep impurity removal. The invention not only solves the problem of resource treatment of the fused salt chlorination slag, realizes cyclic utilization of NaCl fused salt chlorination, but also breaks through the equilibrium cycle of Cl elements in the fused salt chlorination industry-chlor-alkali chemical industry, realizes high-efficiency utilization of Panxi titanium resources, and has great significance for developing and utilizing titanium resources in China and native titanium resources in the world.
Description
Technical Field
The invention relates to a method for recycling molten salt chlorination residues, recycling recovered NaCl and deeply refining NaCl brine for ionic membrane caustic soda, belonging to the technical fields of waste salt treatment in the production field of titanium tetrachloride and deep refining of chlor-alkali chemical brine.
Background
95 percent of titanium resources in China are primary titaniferous ores (about 80 percent of global titanium resources are primary titaniferous ores), titanium slag smelted by taking the primary titaniferous ores (such as Panxi vanadium titano-magnetite) as initial resources is generally high in calcium and magnesium (MgO + CaO is more than or equal to 7 percent), and TiO2Low grade (74-76 percent), can not be used as raw materials for boiling chlorination production, and only can adopt a molten salt chlorination method to produce TiCl4Further producing sponge titanium and titanium white chloride. Years of production practice of domestic enterprises shows that the molten salt chlorination method has obvious cost advantage compared with the boiling method. However, the production amount of waste salt (molten salt chlorination slag) of molten salt chlorination is large, the components are complex, and the treatment and utilization are difficult. At present, the treatment is generally carried out at home and abroad by adopting a filling cooling-crushing-lime mixing special slag yard landfill mode, and more than 80 percent of components of the treatment are soluble metal chlorides, so that the risk of soil and underground water pollution is great, the technical problem of neck clamping for survival and development of a molten salt chlorination process is formed, and the problem needs to be solved urgently.
After the molten salt chlorination slag is subjected to resource treatment, the recovered NaCl amount is larger than that required by molten salt chlorination, and the problem of excessive NaCl output required by the molten salt chlorination needs to be solved. The best way to solve the problem is to directly use NaCl brine prepared from the fused salt chlorination residues for the production of the ionic membrane caustic soda. However, the amount of associated elements of the Panxi titanium resource is large (more than 20), 26 elements in the brine recovered from the fused salt chlorination slag can not meet the control requirement of impurity elements in the brine in the ionic membrane caustic soda tank, and the deep removal problem of Cr, V, Ti, As, Sb and the like (<20ppb) can not be realized by adopting the prior brine pretreatment technology matched with the ionic membrane caustic soda.
Disclosure of Invention
The invention aims to solve the technical problems of resource treatment of the fused salt chlorination residues and effective NaCl circulation.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag together comprises the following steps:
a. leaching: leaching the fused salt chlorination residues with water, and filtering after complete leaching to obtain crude salt water;
b. preparing mixed brine: adding an oxidant and a precipitator into the crude brine under stirring, and precipitating and filtering after complete reaction to obtain mixed brine; the oxidant is NaClO solution or NaClO-containing alkaline solution; the precipitant is NaOH or Na2CO3、NaHCO3At least one of;
c. preparing magnesium-removed NaCl brine: adding a sodium carbonate solution into the mixed brine, heating to the temperature of more than 80 ℃ for reaction, standing after the reaction is completed, and filtering to obtain magnesium-removed NaCl brine;
d. preparing a NaCl product and drying for recycling in a molten salt chlorination furnace: taking part of the magnesium-removed NaCl brine for evaporation and crystallization to prepare a NaCl product, and returning the dried NaCl product to the molten salt chlorination furnace for recycling in molten salt chlorination; the amount of the magnesium-removed NaCl brine for evaporative crystallization is determined according to the amount of NaCl required by the molten salt chlorination furnace;
e. preparing primary brine saturated by caustic soda through an ionic membrane: taking the other part of the magnesium-removed NaCl brine and the light brine generated by chlor-alkali to be directly sent into a salt dissolving pool of an ionic membrane caustic soda plant, adding raw salt into the salt dissolving pool until the NaCl reaches 315g/L, settling and clarifying, wherein the supernatant is the primary brine;
f. deeply reducing and removing impurities: adding a composite reduction precipitator into the primary saline water, settling after reaction, and filtering supernatant through a ceramic membrane filter; the composite reducing agent comprises 0-90% of sodium pyrosulfite, 0-60% of sodium sulfide and Na2CO35-20% of other inorganic additives and 0-20% of other inorganic additives;
g. synergistic removal of Mg2+、CO3 2-、SO4 2-Plasma: adding soda lime into the brine obtained in the step f to adjust the pH value to be more than or equal to 11.6, and then adding FeCl3After reaction and standing, filtering by a precision filter;
h. neutralizing, filtering and removing impurities: adding hydrochloric acid into the saline water obtained in the step g to adjust the pH value to be 8.0-9.7, and adding FeCl3Filtering the supernatant after the reaction by using a ceramic membrane to obtain a filtrate, namely qualified primary brine;
i. deeply removing impurities: and (5) sending the primary saline water obtained in the step h into a chelating resin adsorption tower special for the ionic membrane caustic soda, and sending the produced saline water into an ionic membrane electrolytic cell for electrolysis.
Wherein, in the method, Cl generated by electrolysis in the step i2The method is used for molten salt chlorination, wherein one part of liquid alkali is used for concentration and one part of liquid alkali is used for external sales, and the other part of liquid alkali is used for absorption and purification of tail gas of a molten salt chlorination furnace, water quenching flue gas and waste chlorine generated in caustic soda production; and waste brine generated by tail gas and flue gas purification and waste alkali liquor generated by waste chlorine absorption are used for oxidation and impurity removal of mixed brine.
Wherein, the sequence of the primary brine impurity removal steps can be adjusted according to different processes of salt dissolving in chlor-alkali plants and brine pretreatment.
In the step a of the method, the mass ratio of water to the molten salt chlorination slag is more than or equal to 1.8.
In the step b, the dosage of the oxidant and the precipitant is 1.1-1.5 times of the mole number of the TFe in the crude brine.
In the step d of the method, the condensed water obtained by evaporation and crystallization is circularly used for washing and purifying the solid product, and the washing water is used as the leaching supplementing water in the step a.
In the step f of the method, the addition amount of the composite reduction precipitator is 200-400 mg/l.
Wherein, in step f of the method, the other inorganic auxiliary agent is FeCl2And the like.
Wherein, in step g of the above method, FeCl3The amount of (B) was added in a concentration of 50mg/l after the addition.
Wherein, in step h of the above method, FeCl3The addition amount of (b) is added according to the concentration of 50mg/l after the addition; the reaction time is more than or equal to 12 hours.
The invention has the beneficial effects that: the invention not only solves the problem of resource treatment of the fused salt chlorination slag, but also provides a stable deep refining process of the recovered brine, and solves the problem that the recovered brine is used for producing Cr, V, Ti, Pb, Al, Sb and CO in the ionic membrane caustic soda production3 2-、F-And waiting more than 20 kinds of ion deep refining and removing technical problems. The method not only realizes the cyclic utilization of NaCl fused salt chlorination, effectively recovers the resources of Fe, Mn and Mg in the titanium slag raw material of fused salt chlorination furnace through preparing the ferric hydroxide mixture and the basic magnesium carbonate, but also breaks through the equilibrium cycle of Cl element in the fused salt chlorination industry-chlor-alkali chemical industry, and realizes the efficient utilization of Panxi titanium resource. The invention has great significance for developing and utilizing titanium resources in China and global native titanium resources.
Drawings
FIG. 1 is a schematic flow chart of one embodiment of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1:
the mass ratio of slag to water in the waste molten salt leaching is 1: 2.1, the oxidation impurity removal oxidation precipitator adopts waste brine and waste alkali liquor, the volume ratio of the waste brine to the waste alkali liquor to the crude brine is 1.2: 1(v/v), the active chlorine in the waste brine and the waste alkali liquor is 8.2g/l, and the reaction time is 14 h. One third of the magnesium-removed brine is evaporated and crystallized by MVR, the purity of NaCl dry basis is 98.9 percent, the dried magnesium-removed brine returns to a molten salt chlorination furnace, and the molten salt chlorination production is not abnormal. And the other two thirds of the saline water is sent to an ionic membrane burning and alkalizing salt workshop, the adding amount of the composite reduction precipitator in the initial saline water is about 220mg/l, and the ceramic membrane filtration is carried out after the reaction is carried out for 8 hours. Adding 20% soda lime slurry into the filtrate, adjusting the pH of the solution to 12.0, reacting and precipitating for 4h, and filtering. Adding FeCl 50mg/l into the filtrate3Adjusting pH to 8.6 with high-purity hydrochloric acid, adding 50mg/l FeCl3Reacting and precipitating for 12h, pumping the supernatant into a chelating resin adsorption tower, and discharging Fe, Mn, Cu, Ni and A in water22 elements such as s, Ca2+, Mg2+, Sr2+, Cr, V, Al, Sn, Zn, Pb, Ti and the like are below 20ppb, and CO is3 2-、SO4 2-Respectively controlled below 0.5g/l and 0.2 g/l. The electrolysis operation is not abnormal, and the quality of NaOH products is not abnormal.
Fe (OH) in the recovered mixed dry basis of iron hydroxide3About 72.8%, Mn (OH)4About 12.2 percent of CaO, about 2.1 percent of CaO, about 6.1 percent of basic magnesium carbonate, TiO2About 2.8%, C about 1.4%, SiO2About 2.1, S0.04%, P0.01%. Calcining at 600 ℃ for 2h to obtain metallurgical raw materials with TFe of about 54.9 percent and Mn9.4 percent. The recovered basic magnesium carbonate dry basis meets the requirements of HG/T2959-2010 equal quality.
Example 2:
the mass ratio of slag to water in the waste molten salt leaching is 1: 1.9, the oxidation impurity removal oxidation precipitator adopts waste salt water and waste alkali liquor, and the volume ratio of the waste salt water to the waste alkali liquor is as follows: the crude salt water is 1.4:1(v/v), the waste salt water and the active chlorine in the waste alkali liquor are 16g/l, and the reaction time is 20 h. One third of the magnesium-removed brine is evaporated and crystallized by MVR, the purity of NaCl dry basis is 99.1 percent, the dried magnesium-removed brine returns to a molten salt chlorination furnace, and the molten salt chlorination production is not abnormal. And the other two thirds of the saline water is sent to an ionic membrane burning alkalization salt workshop, the adding amount of the composite reduction precipitator in the initial saline water is about 240mg/l, and the ceramic membrane filtration is carried out after the reaction is carried out for 9 hours. Adding 20% soda lime slurry into the filtrate, adjusting the pH of the solution to 11.8, reacting and precipitating for 4h, and filtering. Adding FeCl 50mg/l into the filtrate3Adjusting pH to 9.1 with high-purity hydrochloric acid, adding 50mg/l FeCl3Reacting and precipitating for 12h, pumping the supernatant into a chelating resin adsorption tower, and discharging Fe, Mn, Cu, Ni, As and Ca in water2+、Mg2+、Sr2+22 Cr, V, Al, Sn, Zn, Pb, Ti, etc. are all below 20ppb, CO3 2-、SO4 2-Respectively controlled below 0.4g/l and 0.3 g/l. The electrolysis operation is not abnormal, and the quality of NaOH products is not abnormal.
Fe (OH) in the recovered mixed dry basis of iron hydroxide3About 74.6%, Mn (OH)4About 11.42 percent of CaO, about 2.3 percent of CaO, about 6.6 percent of basic magnesium carbonate, TiO2About 2.5%, C about 1.2%, SiO2About 2.4, S0.06%, P0.03%. Calcination at 600 deg.C2h, obtaining metallurgical raw materials with TFe of about 55.7 percent and Mn8.6 percent. The recovered basic magnesium carbonate dry basis meets the requirements of HG/T2959-2010 equal quality.
Claims (8)
1. A method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag together is characterized by comprising the following steps:
a. leaching: leaching the fused salt chlorination residues with water, and filtering after complete leaching to obtain crude salt water;
b. preparing mixed brine: adding an oxidant and a precipitator into the crude brine under stirring, and precipitating and filtering after complete reaction to obtain mixed brine; the oxidant is NaClO solution or NaClO-containing alkaline solution; the precipitant is NaOH or Na2CO3、NaHCO3At least one of;
c. preparing magnesium-removed NaCl brine: adding a sodium carbonate solution into the mixed brine, heating to the temperature of more than 80 ℃ for reaction, standing after the reaction is completed, and filtering to obtain magnesium-removed NaCl brine;
d. preparing a NaCl product and drying for recycling in a molten salt chlorination furnace: taking part of the magnesium-removed NaCl brine for evaporation and crystallization to prepare a NaCl product, and returning the dried NaCl product to the molten salt chlorination furnace for recycling in molten salt chlorination; the amount of the magnesium-removed NaCl brine for evaporative crystallization is determined according to the amount of NaCl required by the molten salt chlorination furnace;
e. preparing primary brine saturated by caustic soda through an ionic membrane: taking the other part of the magnesium-removed NaCl brine and the light brine generated by chlor-alkali to be directly sent into a salt dissolving pool of an ionic membrane caustic soda plant, adding raw salt into the salt dissolving pool until the NaCl reaches 315g/L, settling and clarifying, wherein the supernatant is the primary brine;
f. deeply reducing and removing impurities: adding a composite reduction precipitator into the primary saline water, settling after reaction, and filtering supernatant through a ceramic membrane filter; the composite reducing agent comprises 0-90% of sodium pyrosulfite, 0-60% of sodium sulfide and Na2CO35-20% of other inorganic additives and 0-20% of other inorganic additives;
g. synergistic removal of Mg2+、CO3 2-、SO4 2-Plasma: adding soda lime into the brine obtained in the step f to adjust the pH value to be more than or equal to 11.6, and then addingFeCl3After reaction and standing, filtering by a precision filter;
h. neutralizing, filtering and removing impurities: adding hydrochloric acid into the saline water obtained in the step g to adjust the pH value to be 8.0-9.7, and adding FeCl3Filtering the supernatant after the reaction by using a ceramic membrane to obtain a filtrate, namely qualified primary brine;
i. deeply removing impurities: and (5) sending the primary saline water obtained in the step h into a chelating resin adsorption tower special for the ionic membrane caustic soda, and sending the produced saline water into an ionic membrane electrolytic cell for electrolysis.
2. The method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag according to claim 1, which is characterized in that: cl produced by electrolysis in step i2The method is used for molten salt chlorination, wherein one part of liquid alkali is used for concentration and one part of liquid alkali is used for external sales, and the other part of liquid alkali is used for absorption and purification of tail gas of a molten salt chlorination furnace, water quenching flue gas and waste chlorine generated in caustic soda production; and waste brine generated by tail gas and flue gas purification and waste alkali liquor generated by waste chlorine absorption are used for oxidation and impurity removal of mixed brine.
3. The method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag according to claim 1, which is characterized in that: in the step a, the mass ratio of water to molten salt chlorination slag is more than or equal to 1.8.
4. The method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag according to claim 1, which is characterized in that: in the step b, the dosage of the oxidant and the precipitator is 1.1-1.5 times of the mole number of TFe in the crude brine.
5. The method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag according to claim 1, which is characterized in that: in the step d, the condensed water obtained by evaporation and crystallization is circularly used for washing and purifying the solid product, and the washing water is used as the leaching supplementing water in the step a.
6. The method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag according to claim 1, which is characterized in that: in the step f, the addition amount of the composite reduction precipitator is 200-400 mg/l.
7. The method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag according to claim 1, which is characterized in that: in step g, FeCl3The amount of (B) was added in a concentration of 50mg/l after the addition.
8. The method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag according to claim 1, which is characterized in that: in step h, FeCl3The addition amount of (b) is added according to the concentration of 50mg/l after the addition; the reaction time is more than or equal to 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111142929.4A CN113816399A (en) | 2021-09-28 | 2021-09-28 | Method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111142929.4A CN113816399A (en) | 2021-09-28 | 2021-09-28 | Method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113816399A true CN113816399A (en) | 2021-12-21 |
Family
ID=78915766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111142929.4A Pending CN113816399A (en) | 2021-09-28 | 2021-09-28 | Method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113816399A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835309A (en) * | 2021-12-22 | 2022-08-02 | 朱臻 | Waste salt recovery equipment for chlor-alkali chemical production and recovery method thereof |
| 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 |
| CN118142513A (en) * | 2024-05-09 | 2024-06-07 | 成都先进金属材料产业技术研究院股份有限公司 | Molten salt chloride slag resource utilization method, denitration catalyst and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235510A (en) * | 2007-11-08 | 2008-08-06 | 山东海化氯碱树脂有限公司 | Method for removing SO4(2-) ion in ionic film electrolysis sodium hydroxide light salt water |
| US20140069821A1 (en) * | 2012-05-23 | 2014-03-13 | High Sierra Energy, LP | System and method for treatment of produced waters |
| CN105883911A (en) * | 2016-04-07 | 2016-08-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Resourceful treatment method for fused salt chlorination residues |
| CN107164637A (en) * | 2017-06-30 | 2017-09-15 | 江苏省冶金设计院有限公司 | The system and method for handling titanium dioxide fused salt chlorimation abraum salt |
| CN110282637A (en) * | 2019-07-30 | 2019-09-27 | 南京纳亿工程技术有限公司 | A method of improving Galuber's salt type brine dosage in ion film caustic soda processed |
| CN110342548A (en) * | 2019-07-30 | 2019-10-18 | 南京纳亿工程技术有限公司 | A kind of method that ion film caustic soda primary purification salt water removes sial deep refining |
| CN113213510A (en) * | 2021-04-26 | 2021-08-06 | 攀钢集团攀枝花钛材有限公司 | Method for treating waste salt generated by chlorination of molten salt |
-
2021
- 2021-09-28 CN CN202111142929.4A patent/CN113816399A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235510A (en) * | 2007-11-08 | 2008-08-06 | 山东海化氯碱树脂有限公司 | Method for removing SO4(2-) ion in ionic film electrolysis sodium hydroxide light salt water |
| US20140069821A1 (en) * | 2012-05-23 | 2014-03-13 | High Sierra Energy, LP | System and method for treatment of produced waters |
| CN105883911A (en) * | 2016-04-07 | 2016-08-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Resourceful treatment method for fused salt chlorination residues |
| CN107164637A (en) * | 2017-06-30 | 2017-09-15 | 江苏省冶金设计院有限公司 | The system and method for handling titanium dioxide fused salt chlorimation abraum salt |
| CN110282637A (en) * | 2019-07-30 | 2019-09-27 | 南京纳亿工程技术有限公司 | A method of improving Galuber's salt type brine dosage in ion film caustic soda processed |
| CN110342548A (en) * | 2019-07-30 | 2019-10-18 | 南京纳亿工程技术有限公司 | A kind of method that ion film caustic soda primary purification salt water removes sial deep refining |
| CN113213510A (en) * | 2021-04-26 | 2021-08-06 | 攀钢集团攀枝花钛材有限公司 | Method for treating waste salt generated by chlorination of molten salt |
Non-Patent Citations (1)
| Title |
|---|
| 彭银仙: "《化学工艺学》", vol. 2018, 哈尔滨工程大学出版社, pages: 149 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835309A (en) * | 2021-12-22 | 2022-08-02 | 朱臻 | Waste salt recovery equipment for chlor-alkali chemical production and recovery method thereof |
| 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 |
| CN118142513A (en) * | 2024-05-09 | 2024-06-07 | 成都先进金属材料产业技术研究院股份有限公司 | Molten salt chloride slag resource utilization method, denitration catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113816399A (en) | Method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag | |
| WO2017174012A1 (en) | Molten-salt chlorinated-slag resource processing method | |
| CN108372185B (en) | Titanium chloride slag resource utilization method and device | |
| CN105129822B (en) | System and method for treating chlor-alkali production byproduct salt mud | |
| CN101066827B (en) | Electroplating sludge treating and utilizing process | |
| CN102070198A (en) | Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron | |
| CN104016398B (en) | A kind of method that dilute sulfuric acid utilized in industrial wastewater produces sulfate | |
| CN107500352B (en) | A kind of method that low-temperature precipitation produces high-purity ammonium vanadate | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN106277005B (en) | A kind of method that ice crystal, calcium carbonate and sodium sulphate are reclaimed in the resource from calcium fluoride sludge | |
| CN111661972A (en) | Process for treating and recycling lead-zinc smelting flue gas washing waste acid | |
| CN110436595A (en) | A kind of processing method of rare-earth industry waste water | |
| CN101760637B (en) | Leaching technology of magnesium-containing ore | |
| CN112279277A (en) | System and method for high-end resource utilization of flue gas desulfurization by magnesium method | |
| CN111115673A (en) | Method for utilizing all components of caustic sludge | |
| CN103122411B (en) | Cyclic and comprehensive utilization method of sodium-free mangano-manganic oxide production mother solution | |
| CN109694092A (en) | A kind of comprehensive processing method of the solid waste containing chlorine | |
| CN107140660B (en) | A kind of preparation method of potassium carbonate | |
| CN101760638B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN108118143A (en) | Two sections of chloridising roastings-alkaline leaching method puies forward the method that lithium prepares lithium carbonate from lepidolite | |
| CN111424168A (en) | Water-washing dechlorination system and method for metallurgical precipitator dust | |
| CN107337216A (en) | A kind of method that potassium feldspar hydro-thermal alkaline process prepares potassium hydroxide | |
| CN106746402B (en) | Method for treating arsenic-removing sludge | |
| CN112897560B (en) | Coal gangue preparation method method for purifying alumina | |
| CN113697834B (en) | Method for preparing friedel-crafts salt from titanium extraction slag and friedel-crafts salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211221 |