CN114162861B - Synthetic rutile mother liquor comprehensive utilization method - Google Patents
Synthetic rutile mother liquor comprehensive utilization method Download PDFInfo
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- CN114162861B CN114162861B CN202111652623.3A CN202111652623A CN114162861B CN 114162861 B CN114162861 B CN 114162861B CN 202111652623 A CN202111652623 A CN 202111652623A CN 114162861 B CN114162861 B CN 114162861B
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 151
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000007790 solid phase Substances 0.000 claims abstract description 112
- 239000002253 acid Substances 0.000 claims abstract description 82
- 238000002386 leaching Methods 0.000 claims abstract description 71
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000010936 titanium Substances 0.000 claims abstract description 63
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000126 substance Substances 0.000 claims abstract description 34
- 239000002699 waste material Substances 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 20
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010413 mother solution Substances 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 68
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004537 pulping Methods 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000001465 metallisation Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- 230000001276 controlling effect Effects 0.000 description 14
- 235000010215 titanium dioxide Nutrition 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a synthetic rutile mother liquor comprehensive utilization method, which comprises the following steps: s1, adding reduced titanium into an artificial rutile mother solution, performing primary leaching reaction, and performing solid-liquid separation after the reaction to obtain primary mother solution and a solid phase A; s2, the primary mother liquor is subjected to microporous filtration with the aperture of 0.5-2 mu m to obtain secondary mother liquor and a solid phase substance B; regulating the temperature of the secondary mother liquor to 60-80 ℃, carrying out hydrolysis reaction, and after the reaction is finished, carrying out solid-liquid separation to obtain purified mother liquor and a solid-phase metatitanic acid substance C; s3, carrying out oxidation reaction on the purification mother liquor to obtain iron oxide black; and preparing trivalent titanium from the metatitanic acid solid phase C. The method adopts the reduced titanium, can reduce the acidity of the synthetic rutile mother liquor without iron powder consumption, effectively reduces the production cost and reduces the waste of resources.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a synthetic rutile mother liquor comprehensive utilization method.
Background
The method has the advantages that the production flow of the titanium white by the chlorination method is short, the production capacity is easy to expand, the continuous automation degree is high, the product quality control is stable compared with the sulfuric acid method, the three wastes are less, the environmental protection problem is less, the method is a main production technology of the titanium white, the raw materials are mainly artificial rutile, the method for preparing the artificial rutile by adopting the titanium white waste acid to leach and reduce ilmenite is adopted, the prepared artificial rutile has low cost, good quality, large yield and low equipment requirement, but the problem that the artificial rutile mother liquor separated after leaching is difficult to treat exists, and the artificial rutile mother liquor by the hydrochloric acid method contains a large amount of FeCl 2 、FeCl 3 、TiOCl 2 And unreacted HCl, and also small amounts of metal ions such as calcium, magnesium, etc. If the obtained synthetic rutile mother liquor can not be reasonably treated or utilized, the development of the method is directly restrained.
An artificial rutile mother liquor separated from artificial rutile prepared by leaching and reducing ilmenite by sulfuric acid process titanium dioxide waste acid contains a large amount of FeSO 4 、Fe 2 (SO 4 ) 3 、TiOSO 4 And unreacted H 2 SO 4 Etc. Because the concentration of ferrous sulfate in the mother solution is higher, if the ferrous sulfate is directly crystallized, the solubility of the ferrous sulfate is higher, and the crystallization rate of ferrous sulfate heptahydrate is only about 30 percent; the concentration crystallization is adopted, so that the equipment requirement is high, the equipment investment cost is high and the operation cost is high; meanwhile, the synthetic rutile mother liquor contains a small amount of acid, impurities and the like, which can influence the application of the later-stage mother liquor and cause higher production cost of the later-stage application; and the direct neutralization consumes a large amount of limestone or carbide sludge to generate a large amount of yellow sludge, which is difficult to use and causes resource waste.
In the prior art, many research reports have been developed on the treatment of synthetic rutile mother liquor by a chlorination process and a sulfuric acid process.
As patent CN202010457199.6 discloses a method for treating synthetic rutile mother liquor, which adds the synthetic rutile mother liquor of hydrochloric acid method into reduced titanium to make leaching reaction, after the reaction is finished, solid-liquid separation is carried out to obtain mother liquor and solid phase material, and the solid phase material is calcined to obtain the synthetic rutile. The patent adopts reduced titanium as a treating agent, reduces the content of residual acid in mother liquor, and the obtained solid phase material is qualified titanium-rich material without new acid leaching. However, the mother liquor treated by the patent still has high concentration of residual acid, further treatment is still needed, and Fe ions in the mother liquor are not recycled.
As patent CN202011199684.4 discloses a method for utilizing synthetic rutile mother liquor, which comprises the steps of firstly reacting synthetic rutile mother liquor of sulfuric acid method with calcium chloride to obtain gypsum and ferrous chloride solution, then adding alkali into ferrous chloride to obtain ferrous hydroxide, and then calcining to obtain iron concentrate. The patent recovers and utilizes both the residual acid and Fe ions in the mother liquor, but consumes a large amount of calcium chloride.
Disclosure of Invention
The invention aims to provide a novel synthetic rutile mother liquor comprehensive utilization method for solving the defects in the prior art.
The invention aims at realizing the following technical scheme:
a synthetic rutile mother liquor comprehensive utilization method comprises the following steps:
s1, adding reduced titanium into an artificial rutile mother solution, performing primary leaching reaction, and performing solid-liquid separation after the reaction to obtain primary mother solution and a solid phase A; the mass percentage concentration of sulfuric acid in the primary mother liquor is less than 1%; the solid phase A is added with waste acid to carry out secondary leaching reaction to obtain synthetic rutile;
s2, the primary mother liquor is subjected to microporous filtration with the aperture of 0.5-2 mu m to obtain secondary mother liquor and a solid phase substance B; the secondary mother liquor is adjusted to 60-80 ℃ for hydrolysis reaction for 40-100 min, and after the reaction is finished, the purified mother liquor and the metatitanic acid solid phase C are obtained through solid-liquid separation; the solid phase B is added with waste acid to carry out secondary leaching reaction to obtain synthetic rutile;
s3, carrying out oxidation reaction on the purification mother liquor to obtain iron oxide black; and preparing trivalent titanium from the metatitanic acid solid phase substance C.
Preferably, the steps ofThe primary leaching reaction in the step S1 is carried out at the leaching temperature of 55-65 ℃ for 2-4 h, the mass to volume ratio of the reduced titanium to the synthetic rutile mother solution is 1:8-11, and t:m 3 The method comprises the steps of carrying out a first treatment on the surface of the The metallization rate of iron in the reduced titanium is 65-85%, TFe in the reduced titanium is more than or equal to 30%, and TiO 2 More than or equal to 55 percent; the mass percentage concentration of sulfuric acid in the synthetic rutile mother liquor is 4-8%.
Preferably, the secondary leaching reaction conditions in steps S1 and S2 are: the mass fraction of sulfuric acid in the waste acid is 16-18%, the leaching temperature is 55-80 ℃, the leaching reaction time is 2-4 h, and the mass to volume ratio of solid phase matters to the waste acid is 1:3-5, t:m 3 。
Preferably, the step of oxidizing the purified mother liquor in the step S3 to obtain iron oxide black includes:
the pH value of the purified mother liquor is adjusted to be 4-6, then air is introduced, the temperature of the system is adjusted to be 75-95 ℃, and the temperature is kept for 4-8 hours; the air flow is 0.2-2 m 3 Per min per cubic meter of material.
Preferably, the step of preparing trivalent titanium from the metatitanic acid solid phase substance C in the step S3 includes:
washing the solid phase C of the metatitanic acid with water, pulping, adding sulfuric acid, heating until the metatitanic acid is completely dissolved, cooling and supplementing water, and adding elemental aluminum to react to obtain trivalent titanium.
Preferably, the metatitanic acid solid phase C is prepared by TiO 2 The dosage ratio of the water to the water is 1:30-35, t:m 3 。
Preferably, the sulfuric acid is concentrated sulfuric acid with the mass percentage concentration of more than 95%, the addition amount is 5-8 times of the mass of the solid-phase meta-titanate C, the addition amount of the simple substance aluminum is 0.15-0.20 times of the mass of the solid-phase meta-titanate C, wherein the mass of the solid-phase meta-titanate C is TiO 2 And (5) counting.
Preferably, step S3 uses sodium carbonate, sodium hydroxide or ammonia to adjust the pH.
Compared with the prior art, the application has the following beneficial effects:
1. the method adopts the reduced titanium, so that the acidity of the synthetic rutile mother liquor can be reduced without iron powder consumption, the production cost is effectively reduced, and the waste of resources is reduced;
2. the method improves the concentration of iron ions in the primary mother liquor, can produce more ferric oxide pigment under the condition of consuming the mother liquor with the same volume, reduces the concentration of sulfuric acid in the primary mother liquor, and can reduce the consumption of sodium carbonate in the preparation process of the ferric oxide pigment;
3. the application adopts microporous filtration to recycle the solid phase material B, and compared with the traditional mode of adding flocculant and removing impurities by activated carbon, the solid phase material B can be reused for production without introducing new impurities. Meanwhile, the metatitanic acid solid phase substance C is used for producing trivalent titanium for waste utilization, so that no harmful substances are discharged in the whole process, and the synthetic rutile mother liquor is fully utilized.
Compared with the patent CN202011199684.4, the method can recycle the iron, the titanium and the waste acid in the synthetic rutile mother liquor without consuming alkali and a large amount of calcium chloride; compared with the patent CN202010457199.6, the acidity of the mother liquor can be reduced, and Fe ions in the mother liquor can be recycled.
Detailed Description
The synthetic rutile mother liquor comprehensive utilization method provided by the invention comprises the following steps:
s1, adding reduced titanium into an artificial rutile mother solution, performing primary leaching reaction, and performing solid-liquid separation after the reaction to obtain primary mother solution and a solid phase A; the mass percentage concentration of sulfuric acid in the primary mother liquor is less than 1%; the solid phase material A is mainly reduced titanium containing elemental iron, and waste acid can be added for secondary leaching reaction to obtain synthetic rutile, so that titanium resources are fully recycled;
s2, the primary mother liquor is subjected to microporous filtration with the aperture of 0.5-2 mu m to obtain secondary mother liquor and a solid phase substance B; regulating the temperature of the secondary mother liquor to 60-80 ℃, carrying out hydrolysis reaction for 40-100 min, and after the reaction is finished, carrying out solid-liquid separation to obtain purified mother liquor and a metatitanic acid solid phase substance C; after solid-liquid separation, most of the reduced titanium which is not completely reacted enters a solid phase A, but a small amount of small particle matters still remain in the primary mother liquor, and the small particle matters can be effectively separated through microporous filtration to obtain a secondary mother liquor and a solid phase B, and the solid phase B can be added with waste acid to carry out secondary leaching reaction to obtain the synthetic rutile; after the secondary mother solution is hydrolyzed, the soluble titanium is hydrolyzed into a water-insoluble metatitanic acid solid phase;
s3, carrying out oxidation reaction on the purification mother liquor to obtain iron oxide black; and preparing trivalent titanium from the metatitanic acid solid phase C.
The main components of the solid phase A and the solid phase B are reduced titanium containing monovalent iron, waste acid is added into the solid phase A and the solid phase B for secondary leaching to obtain synthetic rutile, and titanium and iron resources can be recycled to the greatest extent; the main component of the solid-phase metatitanic acid C is metatitanic acid (containing a small amount of iron) formed after the hydrolysis of soluble titanium, the solid-phase metatitanic acid C is used for preparing trivalent titanium, the trivalent titanium can be used for a sulfuric acid process titanium dioxide bleaching section, titanium resources in the solid-phase metatitanic acid C can be fully utilized, the iron content in the solid-phase metatitanic acid can be removed in the bleaching section, and the adverse effect of the iron content on titanium dioxide is reduced.
Reduced titanium refers to a product obtained by reducing ilmenite, and the main component is TiO 2 And MFe, firstly, adopting reduced titanium to perform primary leaching reaction on the synthetic rutile mother liquor, using iron element in the reduced titanium to consume residual acid in the synthetic rutile mother liquor, effectively reducing sulfuric acid residue in the synthetic rutile mother liquor, obtaining primary mother liquor containing soluble titanyl sulfate and insoluble rutile solid phase A, wherein the residual acid concentration of the primary mother liquor is less than 1%, and then, firstly, carrying out microporous filtration on the primary mother liquor to recover residual reduced titanium particles; and then hydrolyzing the soluble titanyl sulfate into a water-insoluble solid-phase meta-titanic acid substance C and a purification mother solution containing soluble Fe salt, and then respectively treating the solid-phase meta-titanic acid substance C and the purification mother solution to prepare trivalent titanium and ferric oxide black, thereby realizing the recycling of Fe element and titanium element.
Therefore, the invention reduces the acidity of the artificial rutile mother liquor through one-time leaching reaction, compared with the traditional method of adding iron powder to reduce the acidity of the artificial rutile mother liquor, no iron powder is consumed, and the concentration of iron ions in the primary mother liquor is improved by utilizing the acid in the artificial rutile mother liquor and the iron element in the reduced titanium, so that more ferric oxide pigment can be produced under the condition of consuming the same volume of mother liquor, and the reduction of the acidity can reduce the consumption of sodium carbonate in the preparation process of the ferric oxide pigment. After one reaction, the solid phase B is recovered by microporous filtration, and compared with the traditional method of adding flocculant and removing impurities by activated carbon, the solid phase B can be reused for production without introducing new impurities. Meanwhile, the metatitanic acid solid phase substance C is used for producing trivalent titanium for waste utilization, so that no harmful substances are discharged in the whole process, and the synthetic rutile mother liquor is fully utilized.
Preferably, the step S1 is carried out by one leaching reaction, the leaching temperature is 55-65 ℃, the time is 2-4 h, the mass ratio of the reduced titanium to the synthetic rutile mother solution is 1:8-11, and the volume ratio is t:m 3 The method comprises the steps of carrying out a first treatment on the surface of the The metallization rate of iron in the reduced titanium is 65-85%, TFe in the reduced titanium is more than or equal to 30%, and TiO 2 More than or equal to 55 percent; the mass percentage concentration of sulfuric acid in the synthetic rutile mother liquor is 4-8%. Under the condition of primary leaching, the pH of the obtained secondary mother liquor is just in the pH required range of the hydrolysis reaction in the prior art, namely, the pH is 3-5, so that sodium carbonate is not required to be used for regulating the pH of the system during the hydrolysis of the mother liquor as in the prior art.
Preferably, the secondary leaching reaction conditions of steps S1 and S2 are: the mass fraction of sulfuric acid in the waste acid is 16-18%, the leaching temperature is 55-80 ℃, the leaching reaction time is 2-4 h, and the mass to volume ratio of solid phase matters to the waste acid is 1:3-5, t:m 3 . The solid-to-liquid ratio requirement of the secondary leaching reaction is different from that of the primary leaching reaction, because: the artificial rutile mother liquor reacts with excessive reduced titanium during primary leaching, so that the acidity of the mother liquor is reduced, and the concentration of iron ions is improved; and in the secondary leaching process, reacting the solid phase matters leached once with excessive waste sulfuric acid, and completely reacting the simple substance iron in the solid phase matters leached once to obtain the synthetic rutile.
Preferably, the step S3 of purifying the mother liquor for oxidation reaction to obtain iron oxide black comprises the following steps:
the pH value of the purified mother liquor is adjusted to 4-6, then air is introduced, the temperature of the system is adjusted to 75-95 ℃, and the temperature is kept for 4-8 hours; the air flow is 0.2-2 m 3 Per min per cubic meter of material. The pH can be adjusted with sodium carbonate, sodium hydroxide or ammonia.
Preferably, the step S3 of preparing trivalent titanium from the metatitanic acid solid phase C comprises the following steps:
washing the solid phase C of the meta-titanic acid with water, pulping, adding sulfuric acid, heating until the meta-titanic acid is completely dissolved, cooling and supplementing water, and adding elemental aluminum to react to obtain the trivalent titanium.
Preferably, the solid phase of meta-titanic acid C is prepared by TiO 2 The volume ratio of the water to the water washing water is 1:30-35, t:m 3 。
Preferably, the sulfuric acid is concentrated sulfuric acid with the mass percentage concentration of more than 95 percent, the addition amount of the sulfuric acid is 5 to 8 times of the mass of the solid phase C of the meta-titanic acid, and the addition amount of the simple substance aluminum is 0.15 to 0.20 time of the mass of the solid phase C of the meta-titanic acid, wherein the mass of the solid phase C of the meta-titanic acid is TiO 2 Compared with the conventional trivalent titanium preparation process, the iron content of the metatitanic acid solid phase substance C is more than that of the conventional metatitanic acid, and the use level of the simple substance aluminum is slightly increased.
Example 1
(1) 100g of reduced titanium (metallization of iron in reduced titanium 80%, TFe 35%, tiO) 2 60 percent) adding 800mL of artificial rutile mother liquor for primary leaching reaction, wherein the leaching temperature is 55 ℃, after 2 hours of leaching reaction, the solid-liquid separation is carried out after the leaching reaction is finished to obtain primary mother liquor and solid phase A, and the acid content of the primary mother liquor is detected, and the result is shown in a table 1;
(2) The primary mother liquor is subjected to microporous filtration with the pore diameter of 0.5 mu m to obtain secondary mother liquor and a solid phase substance B, and the solid content of the secondary mother liquor is detected, and the result is shown in Table 1; then controlling the temperature of the secondary mother liquor at 80 ℃, preserving heat for 40min to carry out hydrolysis reaction, standing for 4h after the reaction, and filtering to obtain purified mother liquor and a metatitanic acid solid phase substance C;
(3) 90g of solid phase A and solid phase B are added into 270mL of titanium white waste acid (the mass fraction of the waste acid is 17 percent in terms of sulfuric acid), the leaching temperature is 75 ℃, the leaching reaction time is 2 hours, and after the leaching reaction is finished, the solid-liquid separation is carried out to obtain the synthetic rutile mother liquor and the synthetic rutile; returning the synthetic rutile mother liquor to the step S1 for continuous treatment;
(4) 100g of solid phase C of meta-titanic acid (as TiO) were treated with 3L of demineralised water 2 Meter), washing, pulping the washed metatitanic acid solid phase substance into a solution with the concentration of 200g/L, adding 500g of 98% sulfuric acid, heating until the metatitanic acid is completely dissolved, cooling and supplementing water, and adding 15g of aluminum powder to react to obtain a trivalent titanium solution;
(5) 500mL of purified mother liquor was added with sodium carbonate solution to adjust pH to 4, and then air was introduced at an air flow rate of 0.2m 3 And (3) carrying out oxidation reaction at the temperature of 75 ℃ for 6 hours while controlling the temperature of the system per cubic meter of material to obtain the iron oxide black slurry.
Example 2
(1) Adding 100g of reduced titanium into 900mL of artificial rutile mother liquor for primary leaching reaction, wherein the leaching temperature is 60 ℃, after 2 hours of leaching reaction, carrying out solid-liquid separation to obtain primary mother liquor and solid phase A after the leaching reaction is finished, and detecting the acid content of the primary mother liquor, wherein the result is shown in Table 1;
(2) Filtering the primary mother liquor by using microporous filtering equipment with the aperture of 1 μm to obtain secondary mother liquor and solid phase substance B, and detecting the solid content of the secondary mother liquor, wherein the result is shown in Table 1; controlling the temperature of a 500mL secondary mother liquor system at 70 ℃, preserving heat for 50min to carry out hydrolysis reaction, standing for 4.5h after the reaction, and filtering to obtain a purified mother liquor and a metatitanic acid solid phase substance C;
(3) 90g of solid phase A and solid phase B are added into 270mL of titanium white waste acid to carry out secondary leaching reaction, the leaching temperature is 78 ℃, the leaching reaction time is 2h, and after the leaching reaction is finished, the solid-liquid separation is carried out to obtain the synthetic rutile mother liquor and the synthetic rutile; returning the synthetic rutile mother liquor to the step S1 for continuous treatment;
(4) 100g of the solid phase of meta-titanic acid (as TiO) were treated with 3.2L of demineralised water 2 Meter), washing, pulping the washed metatitanic acid solid phase substance into a solution with the concentration of 250g/L, adding 650g of 98% sulfuric acid, heating until the metatitanic acid is completely dissolved, cooling and supplementing water, and adding 18g of aluminum powder to react to obtain a trivalent titanium solution;
(5) 500mL of purified mother liquor was added with sodium carbonate solution to adjust pH to 5, and then air was introduced at an air flow rate of 0.5m 3 And (3) carrying out oxidation reaction at the temperature of the system of 80 ℃ for 5 hours while controlling the temperature of the system per cubic meter of material to obtain the iron oxide black slurry.
Example 3
(1) Pretreatment: adding 100g of reduced titanium into 1000mL of synthetic rutile mother liquor for primary leaching reaction at 58 ℃ for 2 hours, performing solid-liquid separation after the leaching reaction to obtain primary mother liquor and solid phase A, and detecting the acid content of the primary mother liquor, wherein the result is shown in Table 1;
(2) Filtering the primary mother liquor by using microporous filtering equipment with the aperture of 2 mu m to obtain secondary mother liquor and solid phase substance B, and detecting the solid content of the secondary mother liquor, wherein the result is shown in Table 1; controlling the temperature of 500mL of secondary mother liquor at 80 ℃, preserving heat for 50min to carry out hydrolysis reaction, standing for 4h after the reaction, and filtering to obtain purified mother liquor and a solid phase meta-titanic acid substance;
(3) 90g of solid phase A and solid phase B are added into 270mL of titanium white waste acid to carry out secondary leaching reaction, the leaching temperature is 80 ℃, the leaching reaction time is 2h, and after the leaching reaction is finished, the solid-liquid separation is carried out to obtain the synthetic rutile mother liquor and the synthetic rutile; returning the synthetic rutile mother liquor to the step S1 for continuous treatment;
(4) 100g of solid phase C of meta-titanic acid (as TiO) were treated with 3.5L of demineralised water 2 Meter), washing, pulping the washed solid-phase metatitanic acid substance into a solution with the concentration of 300g/L, adding 800g of 98% sulfuric acid, heating until the metatitanic acid is completely dissolved, cooling and supplementing water, and adding 20g of aluminum powder to react to obtain a trivalent titanium solution;
(5) 500mL of purified mother liquor was added with sodium carbonate solution to adjust pH to 4.5, and air was then introduced at an air flow rate of 0.8m 3 And (3) carrying out oxidation reaction at the temperature of 78 ℃ for 5 hours while controlling the temperature of the system per cubic meter of material to obtain the iron oxide black slurry.
Example 4
(1) Pretreatment: adding 100g of reduced titanium into 800mL of artificial rutile mother liquor for primary leaching reaction at 55 ℃ for 2.5 hours, carrying out solid-liquid separation after the leaching reaction to obtain primary mother liquor and solid phase A, and detecting the acid content of the primary mother liquor, wherein the result is shown in Table 1;
(2) Filtering the primary mother liquor by using microporous filtering equipment with the aperture of 0.5 mu m to obtain secondary mother liquor and solid phase B, and detecting the solid content of the secondary mother liquor, wherein the result is shown in Table 1; controlling the temperature of 500mL of secondary mother liquor at 60 ℃, preserving heat for 70min to carry out hydrolysis reaction, standing for 5h after the reaction, and filtering to obtain purified mother liquor and a solid phase meta-titanic acid substance;
(3) 90g of solid phase A and solid phase B are added into 450mL of titanium white waste acid to carry out secondary leaching reaction, the leaching temperature is 80 ℃, the leaching reaction time is 2h, and after the leaching reaction is finished, the solid-liquid separation is carried out to obtain the synthetic rutile mother liquor and the synthetic rutile; returning the synthetic rutile mother liquor to the step S1 for continuous treatment;
(4) 100g of solid phase C of meta-titanic acid (as TiO) were treated with 3.5L of demineralised water 2 Meter), washing, pulping the washed solid-phase metatitanic acid substance into a solution with the concentration of 300g/L, adding 500g of 98% sulfuric acid, heating until the metatitanic acid is completely dissolved, cooling and supplementing water, and adding 20g of aluminum powder to react to obtain a trivalent titanium solution;
(5) 500mL of purified mother liquor was added with sodium carbonate solution to adjust pH to 4, and air was then introduced at an air flow rate of 1.2m 3 And (3) carrying out oxidation reaction at the temperature of 75 ℃ for 4 hours while controlling the temperature of the system per cubic meter of material to obtain the iron oxide black slurry.
Example 5
(1) Pretreatment: adding 100g of reduced titanium into 900mL of artificial rutile mother liquor for primary leaching reaction at a leaching temperature of 56 ℃ for 2.5 hours, carrying out solid-liquid separation after the leaching reaction to obtain primary mother liquor and solid phase A, and detecting the acid content of the primary mother liquor, wherein the result is shown in Table 1;
(2) Filtering the primary mother liquor by using microporous filtering equipment with the aperture of 2 mu m to obtain secondary mother liquor and solid phase substance B, and detecting the solid content of the secondary mother liquor, wherein the result is shown in Table 1; controlling the temperature of 500mL of secondary mother liquor at 80 ℃, preserving heat for 40min to carry out hydrolysis reaction, standing for 5h after the reaction, and filtering to obtain purified mother liquor and a solid phase meta-titanic acid substance;
(3) 90g of solid phase A and solid phase B are added into 270mL of titanium white waste acid to carry out secondary leaching reaction, the leaching temperature is 80 ℃, the leaching reaction time is 2h, and after the leaching reaction is finished, the solid-liquid separation is carried out to obtain the synthetic rutile mother liquor and the synthetic rutile; returning the synthetic rutile mother liquor to the step S1 for continuous treatment;
(4) 100g of solid phase C of meta-titanic acid (as TiO) were treated with 3.5L of demineralised water 2 Meter), washing, pulping the washed solid-phase metatitanic acid substance into a solution with the concentration of 300g/L, adding 800g of 98% sulfuric acid, heating until the metatitanic acid is completely dissolved, cooling and supplementing water, and adding 15g of aluminum powder to react to obtain a trivalent titanium solution;
(5) 500mL of purified mother liquor was added with carbonic acidThe pH of the sodium solution is adjusted to 5, and then air is introduced, and the air flow rate is 0.4m 3 And (3) carrying out oxidation reaction at the temperature of 95 ℃ for 5 hours while controlling the temperature of the system per cubic meter of material to obtain the iron oxide black slurry.
Comparative example 1
(1) Adjusting the pH of the synthetic rutile mother liquor to 3.7 by using a sodium carbonate solution, controlling the system temperature to 60 ℃, preserving heat for 70min to perform hydrolysis reaction, standing for 5h after the reaction, and filtering to obtain a purified mother liquor and a metatitanic acid solid phase substance C;
(2) 100g of solid phase C of meta-titanic acid (as TiO) were treated with 3.5L of demineralised water 2 Meter), washing, pulping the washed solid-phase metatitanic acid substance into a solution with the concentration of 300g/L, adding 500g of 98% sulfuric acid, heating until the metatitanic acid is completely dissolved, cooling and supplementing water, and adding 20g of aluminum powder to react to obtain a trivalent titanium solution;
(3) 500mL of purified mother liquor was added with 75g of ferrous sulfate heptahydrate solid, and then added with sodium carbonate solution to adjust the pH to 4, and then air was introduced to adjust the air flow rate to 1.2m 3 And (3) carrying out oxidation reaction at the temperature of 75 ℃ for 4 hours while controlling the temperature of the system per cubic meter of material to obtain the iron oxide black slurry.
Comparative example 2
(1) Adjusting the pH of the synthetic rutile mother liquor to 3.7 by using a sodium carbonate solution, controlling the system temperature to 60 ℃, preserving heat for 70min to perform hydrolysis reaction, standing for 5h after the reaction, and filtering to obtain a purified mother liquor and a metatitanic acid solid phase substance C;
(2) Piling the metatitanic acid solid phase C;
(3) 500mL of purified mother liquor was added with 75g of ferrous sulfate heptahydrate solid, and then added with sodium carbonate solution to adjust the pH to 4, and then air was introduced to adjust the air flow rate to 1.2m 3 And (3) carrying out oxidation reaction at the temperature of 75 ℃ for 4 hours while controlling the temperature of the system per cubic meter of material to obtain the iron oxide black slurry.
The mother liquor comprehensive utilization and iron oxide black performance of examples 1 to 5 and comparative examples 1 to 2 were analyzed, and the results are shown in tables 1 and 2.
Table 1 comprehensive utilization data table for mother liquor
TABLE 2
As can be seen from the comparison of the data, after the method is used, the acid content of the primary mother liquor is reduced to below 0.1%, the solid content of the secondary mother liquor meets the production requirement, and when the method is used for preparing the iron oxide black slurry, the consumption of ferrous sulfate heptahydrate and alkali liquor is reduced. The trivalent titanium solution prepared by using the solid metatitanic acid solid phase C meets the production index requirement, and solves the problems that the trivalent titanium prepared by using the solid metatitanic acid solid phase C is turbid and cannot be applied to the sulfuric acid process titanium white bleaching process production and can only be piled up for treatment because the solid metatitanic acid solid phase C produced by the prior art contains synthetic rutile and carbon powder.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (4)
1. The synthetic rutile mother liquor comprehensive utilization method is characterized by comprising the following steps:
s1, adding reduced titanium into an artificial rutile mother solution, performing primary leaching reaction, and performing solid-liquid separation after the reaction to obtain primary mother solution and a solid phase A; the mass percentage concentration of sulfuric acid in the primary mother liquor is less than 1%; the solid phase A is added with waste acid to carry out secondary leaching reaction to obtain synthetic rutile; the primary leaching reaction is carried out, and the leaching temperature is 55 to the whole range65 ℃ for 2-4 h, wherein the mass to volume ratio of the reduced titanium to the synthetic rutile mother solution is 1:8-11, t/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The metallization rate of iron in the reduced titanium is 65-85%, TFe in the reduced titanium is more than or equal to 30%, and TiO 2 More than or equal to 55 percent; the mass percentage concentration of sulfuric acid in the synthetic rutile mother liquor is 4-8%;
s2, the primary mother liquor is subjected to microporous filtration with the aperture of 0.5-2 mu m to obtain secondary mother liquor and a solid phase substance B; the secondary mother liquor is adjusted to 60-80 ℃ for hydrolysis reaction for 40-100 min, and after the reaction is finished, the purified mother liquor and the metatitanic acid solid phase C are obtained through solid-liquid separation; the solid phase B is added with waste acid to carry out secondary leaching reaction to obtain synthetic rutile; the secondary leaching reaction conditions in the steps S1 and S2 are as follows: the mass fraction of sulfuric acid in the waste acid is 16-18%, the leaching temperature is 55-80 ℃, the leaching reaction time is 2-4 h, and the mass to volume ratio of solid phase matters to the waste acid is 1:3-5, t:m 3 ；
S3, carrying out oxidation reaction on the purification mother liquor to obtain iron oxide black; preparing trivalent titanium from the metatitanic acid solid phase substance C; the preparation method of the trivalent titanium by the metatitanic acid solid phase substance C comprises the following steps:
washing the solid phase C of the metatitanic acid with water, pulping, adding sulfuric acid, heating until the metatitanic acid is completely dissolved, cooling and supplementing water, and adding elemental aluminum to react to obtain trivalent titanium; the sulfuric acid is concentrated sulfuric acid with the mass percentage concentration of more than 95%, the addition amount of the sulfuric acid is 5-8 times of the mass of the solid-phase meta-titanate substance C, the addition amount of the elemental aluminum is 0.15-0.20 times of the mass of the solid-phase meta-titanate substance C, wherein the mass of the solid-phase meta-titanate substance C is TiO 2 And (5) counting.
2. The synthetic rutile mother liquor comprehensive utilization method according to claim 1, wherein,
the step S3 of oxidizing the purified mother liquor to obtain iron oxide black comprises the following steps:
the pH value of the purified mother liquor is adjusted to be 4-6, then air is introduced, the temperature of the system is adjusted to be 75-95 ℃, and the temperature is kept for 4-8 hours; the air flow is 0.2-2 m 3 Per min per cubic meter of material.
3. The synthetic rutile mother liquor comprehensive utilization method according to claim 1, wherein,
the solid phase C of meta-titanic acid is prepared by TiO 2 The dosage ratio of the water to the water is 1:30-35, t:m 3 。
4. The synthetic rutile mother liquor comprehensive utilization method according to claim 2, wherein,
and step S3, adjusting the pH by adopting sodium carbonate, sodium hydroxide or ammonia water.
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