CN115650311B - Method for removing impurities from titanium dioxide byproduct ferrous sulfate - Google Patents
Method for removing impurities from titanium dioxide byproduct ferrous sulfate Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 108
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 108
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract description 108
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 108
- 239000006227 byproduct Substances 0.000 title claims abstract description 60
- 239000012535 impurity Substances 0.000 title claims abstract description 59
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 131
- 238000003756 stirring Methods 0.000 claims abstract description 110
- 239000011259 mixed solution Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 33
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 33
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 235000010215 titanium dioxide Nutrition 0.000 claims description 58
- 239000010936 titanium Substances 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 3
- 238000005189 flocculation Methods 0.000 claims description 3
- 230000016615 flocculation Effects 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 14
- -1 purity Chemical compound 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 8
- 239000005955 Ferric phosphate Substances 0.000 description 7
- 229940032958 ferric phosphate Drugs 0.000 description 7
- 229910000398 iron phosphate Inorganic materials 0.000 description 7
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a method for removing impurities from ferrous sulfate serving as a titanium dioxide byproduct, which comprises the following steps: s1: taking a titanium dioxide byproduct ferrous sulfate with a certain mass, dissolving the titanium dioxide byproduct ferrous sulfate by using deionized water, heating and stirring to dissolve the titanium dioxide byproduct ferrous sulfate so that the content of the ferrous sulfate is controlled in a certain range, stopping heating when the solute is completely dissolved, cooling and then keeping for a certain time, and filtering insoluble substances; s2: the solution obtained in the step S1 is pumped into a reaction tank to prepare a mixed solution of ammonium bifluoride and ammonium carbonate with multiple concentration gradients, the mixed solution is respectively added into an upper layer and a lower layer along with a hollow stirring paddle, the pH is regulated to a set value, and the mixed solution is stirred for a period of time after heating; s3: adding a certain amount of flocculant into the solution and stirring; s4: filtering the solution in the step S3 by utilizing a filter press to obtain a ferrous sulfate solution with impurities removed, transferring the ferrous sulfate solution into a forming tank, standing for a period of time, and measuring the element content of the ferrous sulfate solution; the method has high stability in the impurity removal process, can greatly remove cationic impurity elements, and can not introduce other impurities.
Description
Technical Field
The invention belongs to the technical field of titanium dioxide byproduct ferrous sulfate impurity removal, and particularly relates to a titanium dioxide byproduct ferrous sulfate impurity removal method.
Background
Titanium dioxide is considered as the white pigment with the best performance at present, and is widely applied to various fields, the production process of titanium dioxide by a sulfuric acid method is relatively simple, the grade requirement on titanium concentrate is not high, and the application in industry is very mature, thus being one of the main production methods of titanium dioxide. At present, larger titanium dioxide enterprises in China basically adopt a sulfuric acid method to produce, and in order to remove ferrous ions partially oxidized after acidolysis process is finished, a proper amount of reduced iron powder is added into titanyl sulfate and ferrous sulfate solution to reduce trivalent iron into bivalent ironIron, and finally, concentrating in vacuum and cooling for crystallization to make all ferrous ions in the titanium liquid in FeSO 4 ·7H 2 O is precipitated in the form of a titanium dioxide by-product ferrous sulfate is produced.
The sulfuric acid process produces a great amount of ferrous sulfate byproducts in the process of producing titanium pigment, and the annual ferrous sulfate yield is up to millions of tons according to incomplete statistics. The content of ferrous sulfate in the titanium white by-product is very high, but the titanium white by-product cannot be directly applied to other fields because of the existence of various impurities such as titanium, manganese, magnesium, aluminum and the like, so that the titanium white by-product is treated as waste, piled up and buried, and not only causes serious pollution to the environment, but also causes huge waste to iron resources. The development of the titanium dioxide industry is limited to a great extent. Therefore, a great deal of work is done by a plurality of researchers at home and abroad on the problem of recycling the byproduct ferrous sulfate, and the shortage is still evident.
In recent years, the China strives for realizing the carbon reaching peak before 2030 and realizing the carbon neutralization before 2060, and the continuous promotion of the work of the carbon reaching peak and the carbon neutralization quickens the development of new energy projects, so that new requirements are provided for further optimizing and adjusting the energy consumption structure, realizing the recycling and efficient utilization of resources and energy sources and constructing a modern energy system with clean low carbon, safety, high efficiency and intelligent interconnection. The market demand of the global lithium battery is rapidly increased, and the lithium ion battery is rapidly developed, so that the development of the lithium battery which takes lithium iron phosphate as a positive electrode material is driven, and the production of the ferric phosphate by taking ferrous sulfate as a titanium dioxide byproduct is a reasonable path. The quality of the electrochemical performance of the lithium iron phosphate is closely related to the quality of precursor ferric phosphate, such as purity, microcosmic morphology, product particle size and the like, and the quality of the ferric phosphate is related to process control and raw material quality. Therefore, iron phosphate with better quality can be controlled from iron phosphate production raw materials, and the aim of removing impurities, refining and purifying the titanium white byproduct ferrous sulfate is particularly important to meet the requirement of an iron source required by the synthesis of iron phosphate and utilize.
The titanium dioxide byproduct ferrous sulfate has various purification process methods, such as hydrolysis precipitation method, directional ultrafiltration method, recrystallization method and the like, but the hydrolysis precipitation method has low cost and simple operation, is suitable for industrial mass production, and is different in that precipitants are used, and impurities entrained in the use process of the precipitants and impurities introduced by the precipitants have influence on the quality, the technological process and the purification efficiency of ferrous sulfate crystal products. In summary, how to use the ferrous sulfate as a byproduct of titanium dioxide to prepare the iron source which meets the requirements of high-quality ferric phosphate becomes a key measure for treating the titanium dioxide byproduct and developing lithium battery materials. Therefore, it is very important to develop a method for refining and purifying titanium dioxide by-products, which is stable, simple to operate and free from impurity introduction.
Disclosure of Invention
The invention aims to solve the problem that the conventional titanium dioxide byproduct ferrous sulfate contains a large amount of impurities such as titanium, magnesium, manganese, aluminum and the like, and provides a stable, simple-operation, impurity substitution-free and low-consumption titanium dioxide byproduct ferrous sulfate impurity removal method which can meet the requirement of serving as a raw material for preparing battery-grade ferric phosphate.
The invention aims to solve the technical problems, and adopts the technical scheme that: a method for removing impurities from titanium dioxide by-product ferrous sulfate comprises the following steps:
s1: taking a titanium dioxide byproduct ferrous sulfate with a certain mass, dissolving the titanium dioxide byproduct ferrous sulfate by using deionized water, heating and stirring to dissolve the titanium dioxide byproduct ferrous sulfate so that the ferrous sulfate content in a ferrous sulfate solution is controlled in a certain range, stopping heating when solute is completely dissolved, cooling the solution and then keeping for a certain time, and filtering out insoluble matters to obtain an unremoved ferrous sulfate solution;
s2: adding the ferrous sulfate solution which is not subjected to impurity removal in the step S1 into a reaction tank to prepare a mixed solution of ammonium bifluoride and ammonium carbonate with multiple concentration gradients, respectively adding the mixed solution into the reaction tank along with a hollow stirring paddle at the upper layer and the lower layer simultaneously, then adjusting the pH value of the solution to a set value by adding the ammonium carbonate solution, heating, stirring for a period of time, and carrying out hydrolysis sedimentation reaction; s3: adding a certain amount of flocculating agent into the solution after the reaction for a period of time, and stirring for a period of time to perform flocculation sedimentation; s4: and (3) filtering the solution in the step S3 by using a filter press to obtain a ferrous sulfate solution after impurity removal, transferring the ferrous sulfate solution into a formation tank, standing for a period of time, and measuring the element content of the ferrous sulfate solution.
Preferably, the titanium dioxide byproduct ferrous sulfate comprises 17.0-20.0% of Fe, 0.4-0.8% of Mg, 0.1-0.4% of Ti and 0.1-0.2% of Mn by mass percent.
Preferably, the heating dissolution temperature of the titanium dioxide byproduct ferrous sulfate in the step S1 is 60 ℃, and the cooling temperature is 45 ℃.
Preferably, the mass percentage of ferrous sulfate in the ferrous sulfate solution in the step S1 is controlled to be 12-15%.
Preferably, in the step S2, the mixed solution A of the ammonium bifluoride and the ammonium carbonate with high concentration gradient is prepared and added at the upper layer along with a hollow stirring paddle in a reaction tank, and the mixed solution B of the ammonium bifluoride and the ammonium carbonate with low concentration gradient is prepared and added at the lower layer along with the hollow stirring paddle in the reaction tank.
Preferably, the mixed solution A is prepared from an ammonium carbonate solution with the mass concentration of 20% and an ammonium bifluoride solution with the mass concentration of 10%, and the mixed solution B is prepared from an ammonium carbonate solution with the mass concentration of 10% and an ammonium bifluoride solution with the mass concentration of 5%; the mass of the finally added ammonium bifluoride is 1.5-2% of the mass of the ferrous sulfate solid serving as the by-product of the titanium dioxide treatment.
Preferably, in the step S2, the pH of the solution is adjusted to 5-5.5 by adding an ammonium carbonate solution with the mass concentration of 10%, then the heating temperature is 60 ℃, the stirring speed is 60r/min, and the stirring time is 20min.
Preferably, in the step S2, the stirring paddles include an upper layer stirring paddle and a lower layer stirring paddle, the upper layer stirring paddle and the lower layer stirring paddle are both hollow pipeline structures which are horizontally arranged, the tail end of each pipeline is open, the head end of each pipeline is communicated with a stirring shaft which is vertically arranged, each stirring shaft is of a hollow pipeline structure, a separation sheet is arranged at the middle part of each stirring shaft, the top of each stirring shaft is communicated with a high-concentration mixed solution feeding pipe through an upper rotary joint, the bottom of each stirring shaft is communicated with a low-concentration mixed solution feeding pipe through a lower rotary joint, the upper side of each stirring shaft is arranged at the top of the reaction tank through a bearing, a first gear is sleeved at the upper end of each stirring shaft, the first gear is meshed with a second gear, and the second gear is arranged on an output shaft of the servo motor; in the feeding process, the mixed solution A enters the upper layer stirring paddle through the high-concentration mixed solution feeding pipe, then comes out from the tail end of the mixed solution A and reaches the upper layer of the reaction tank, and the mixed solution B enters the lower layer stirring paddle through the low-concentration mixed solution feeding pipe and then comes out from the tail end of the mixed solution B and reaches the lower layer of the reaction tank.
Preferably, the flocculant in the step S3 is cationic polyacrylamide, the amount of the flocculant added is six parts per million of the mass of the titanium dioxide byproduct ferrous sulfate in the step S1, the stirring speed is 20r/min, and the stirring time is 10-30min.
Preferably, the filter press in the step S4 is a plate-and-frame filter press.
The invention has the beneficial effects that:
1. compared with the prior art, the impurity removing agent has unique raw materials, the impurity removing agent is a mixed solution with multiple gradient concentrations, the effect is better than that of singly using ammonium bifluoride solution, metal cations, hydroxide and carbonate are combined to form precipitates, the collision combination of anions and cations to be precipitated is quickened by a layered feeding mode, the nucleation speed is improved, meanwhile, precipitates formed after the upper mixed solution A is fed can be settled to a lower layer under the action of gravity, and the lower layer area can be continuously nucleated due to the fact that the original lower layer is added with the low-concentration mixed solution B, the reaction is more thorough, the precipitation is more thorough, the growth speed is quickened by the process, the reaction is more thorough, and the precipitation is completely and fully achieved due to the synergistic effect of concentration differences.
2. In the reaction process, fluoride ions ionized by ammonium bifluoride are combined with magnesium ions in a ferrous sulfate solution to be purified to produce precipitates, an ammonium carbonate solution is ionized to form carbonate ions, bicarbonate ions, ammonium ions and hydroxide ions, magnesium, manganese and aluminum in the ferrous sulfate to be purified are combined under the carbonate ions and the hydroxide ions to produce precipitates, a titanium impurity compound is hydrolyzed to produce metatitanic acid precipitates in the Ph value adjusting process, and ammonium ions and hydroxide ions are combined and then discharged in the form of ammonia gas through heating hydrolysis; therefore, the whole impurity removing agent has no other cations introduced, avoids the risk of bringing other impurity ions into the impurity removing raw materials, provides ideal raw materials for the subsequent production of ferric phosphate and lithium iron phosphate, and reduces the difficulty of impurity element control; the impurity removal process has high stability, can remove cationic impurity elements greatly, can realize industrial production, and has simple operation and low cost.
3. The iron source in the ferrous sulfate solution which is a titanium dioxide byproduct and is prepared in the impurity removal process is 5%, and the residual content in the solution after the impurity removal is more than 4.9%. Can be used as a precursor of battery-grade ferric phosphate.
4. The impurity removal time of the multi-concentration layered adding mode is shortened, the adding mode is unique, a hollow feeding pipeline is arranged in the stirrer, the stirring paddle is used for discharging, the upper and lower layers of concentration difference are used for adding materials, the stirring is a continuous transverse stirring mode, the adding time is shortened due to layered adding, and the reaction time is shortened due to multi-concentration adding and multi-layer reaction.
Drawings
Fig. 1 is a schematic diagram of a stirring paddle and an installation structure thereof, which are related to a method for removing impurities from ferrous sulfate serving as a titanium white byproduct.
Detailed Description
The invention is described in further detail below with reference to the drawings and the specific examples.
A method for removing impurities from titanium dioxide by-product ferrous sulfate comprises the following steps:
s1: taking a titanium dioxide byproduct ferrous sulfate with a certain mass, dissolving the titanium dioxide byproduct ferrous sulfate by using deionized water, heating and stirring to dissolve the titanium dioxide byproduct ferrous sulfate so that the ferrous sulfate content in a ferrous sulfate solution is controlled in a certain range, stopping heating when solute is completely dissolved, cooling the solution and then keeping for a certain time, and filtering out insoluble matters to obtain an unremoved ferrous sulfate solution;
s2: adding the ferrous sulfate solution which is not subjected to impurity removal in the step S1 into a reaction tank 8, preparing a mixed solution of ammonium bifluoride and ammonium carbonate with multiple concentration gradients, respectively adding the mixed solution into the reaction tank 8 along with a hollow stirring paddle 1 at the upper layer and the lower layer simultaneously, then adjusting the pH value of the solution to a set value by adding the ammonium carbonate solution, heating, stirring for a period of time, and carrying out hydrolysis sedimentation reaction;
s3: adding a certain amount of flocculating agent into the solution after the reaction for a period of time, and stirring for a period of time to perform flocculation sedimentation; s4: and (3) filtering the solution in the step S3 by using a filter press to obtain a ferrous sulfate solution after impurity removal, transferring the ferrous sulfate solution into a formation tank, standing for a period of time, and measuring the element content of the ferrous sulfate solution.
Preferably, the titanium dioxide byproduct ferrous sulfate comprises 17.0-20.0% of Fe, 0.4-0.8% of Mg, 0.1-0.4% of Ti and 0.1-0.2% of Mn by mass percent.
Preferably, the heating dissolution temperature of the titanium dioxide byproduct ferrous sulfate in the step S1 is 60 ℃, and the cooling temperature is 45 ℃.
Preferably, the mass percentage of ferrous sulfate in the ferrous sulfate solution in the step S1 is controlled to be 12-15%.
Preferably, in the step S2, the mixed solution a of ammonium bifluoride and ammonium carbonate prepared in a high concentration gradient is added in the upper layer with the hollow stirring paddle 1 in the reaction tank 8, and the mixed solution B of ammonium bifluoride and ammonium carbonate prepared in a low concentration gradient is added in the lower layer with the hollow stirring paddle 1 in the reaction tank 8.
Preferably, the mixed solution A is prepared from an ammonium carbonate solution with the mass concentration of 20% and an ammonium bifluoride solution with the mass concentration of 10%, and the mixed solution B is prepared from an ammonium carbonate solution with the mass concentration of 10% and an ammonium bifluoride solution with the mass concentration of 5%; the mass of the finally added ammonium bifluoride is 1.5-2% of the mass of the ferrous sulfate solid serving as the by-product of the titanium dioxide treatment.
Preferably, in the step S2, the pH of the solution is adjusted to 5-5.5 by adding an ammonium carbonate solution with the mass concentration of 10%, then the heating temperature is 60 ℃, the stirring speed is 60r/min, and the stirring time is 20min. In this embodiment, the mixed solutions a and B have ammonium carbonate solutions therein, so that the effect of adjusting pH can be achieved in advance, and then the pH of the solution is adjusted to 5-5.5 by 10% ammonium carbonate solution.
Preferably, as shown in fig. 1, in step S2, the stirring paddle 1 includes an upper stirring paddle 1.1 and a lower stirring paddle 1.2, the upper stirring paddle 1.1 and the lower stirring paddle 1.2 are hollow pipeline structures which are horizontally arranged, the tail ends of the pipelines are open, the head ends of the pipelines are communicated with a stirring shaft 2 which is vertically arranged, the stirring shaft 2 is of a hollow pipeline structure, a separation sheet 3 is arranged in the middle of the stirring shaft 2, the top of the stirring shaft 2 is communicated with a high-concentration mixed solution feeding pipe 5 through an upper rotary joint 4, the bottom of the stirring shaft 2 is communicated with a low-concentration mixed solution feeding pipe 7 through a lower rotary joint 6, the upper side of the stirring shaft 2 is mounted at the top of a reaction tank 8 through a bearing, a first gear 9 is sleeved at the upper end of the stirring shaft 2, the first gear 9 is meshed with a second gear 10, and the second gear 10 is mounted on an output shaft of a servo motor 11; in the feeding process, the mixed solution A enters the upper stirring paddle 1.1 through the high-concentration mixed solution feeding pipe 5, then comes out from the tail end of the mixed solution A and reaches the upper layer of the reaction tank 8, and the mixed solution B enters the lower stirring paddle 1.2 through the low-concentration mixed solution feeding pipe 7 and then comes out from the tail end of the mixed solution B and reaches the lower layer of the reaction tank 8. In this embodiment, when the servo motor 11 works, the second gear 10 can be driven to rotate, and then the stirring shaft 2 is driven to rotate by the first gear 9, because the top of the stirring shaft 2 is communicated with the high-concentration mixed solution feeding pipe 5 through the upper rotary joint 4, and the bottom of the stirring shaft 2 is communicated with the low-concentration mixed solution feeding pipe 7 through the lower rotary joint 6, when the stirring shaft 2 rotates, the feeding process of the high-concentration mixed solution feeding pipe 5 and the low-concentration mixed solution feeding pipe 7 is not affected, meanwhile, because the stirring shaft 2 is in a hollow pipeline structure, the middle part of the stirring shaft is provided with the separation sheet 3, the feeding processes of the high-concentration mixed solution feeding pipe 5 and the low-concentration mixed solution feeding pipe 7 are not affected by each other, and in addition, in order to prevent material backflow, corresponding one-way valves can be installed on the high-concentration mixed solution feeding pipe 5 and the low-concentration mixed solution feeding pipe 7, so that the problem can be solved; finally, the layering feeding process of the mixed solution A and the mixed solution B can be realized, so that the feeding time and the reaction time can be shortened, and the precipitation reaction rate can be greatly improved.
Preferably, the flocculant in the step S3 is cationic polyacrylamide, the amount of the flocculant added is six parts per million of the mass of the titanium dioxide byproduct ferrous sulfate in the step S1, the stirring speed is 20r/min, and the stirring time is 10-30min.
Preferably, the filter press in the step S4 is a plate-and-frame filter press.
Example 1:
a. taking 250g of titanium dioxide byproduct ferrous sulfate, adding 750g of deionized water for dissolution, enabling the mass fraction of ferrous sulfate solution to be about 13.6%, enabling the iron ion content to be about 5%, heating to 60 ℃, stirring to enable solute to be completely dissolved, stopping heating and cooling to 45 ℃, filtering the solution, and carrying out ICP test.
b. Preparing a multi-gradient concentration mixed solution: mixing solution A:20% ammonium carbonate solution and 10% ammonium bifluoride solution, mixed solution B:10% strength ammonium carbonate solution and 5% strength ammonium bifluoride solution. The mixed solution A enters the upper layer stirring paddle 1.1 through the high-concentration mixed solution feeding pipe 5, then comes out from the tail end of the mixed solution A and reaches the upper layer of the reaction tank 8, the mixed solution B enters the lower layer stirring paddle 1.2 through the low-concentration mixed solution feeding pipe 7, then comes out from the tail end of the mixed solution B and reaches the lower layer of the reaction tank 8, and the adding amount is as follows: 30g of 10% concentration ammonium bifluoride solution and 20g of 5% concentration ammonium bifluoride solution, adding 10% concentration ammonium carbonate solution until the pH of the solution is 5.5, heating to 60 ℃, continuously and transversely stirring at the stirring speed of 60r/min, and reacting for 20min.
c. 0.15g of flocculant was added to the solution, and the stirring speed was 20r/min, and the stirring time was 10min.
d. Filtering the solution, transferring the solution into a standing tank, and taking the ferrous sulfate solution after impurity removal for ICP test.
The test results are shown in Table 1.
Table 1: iron phosphate detection results:
| sample of | Non-impurity-removed ferrous sulfate solution | Ferrous sulfate solution after impurity removal |
| Fe(％) | 5 | 4.95 |
| Na(ppm) | Not detected | Not detected |
| K(ppm) | 11 | 10 |
| Ca(ppm) | 28 | 20 |
| Mg(ppm) | 5264 | 30 |
| Al(ppm) | 45 | 3.5 |
| Zn(ppm) | 63 | 13 |
| Ni(ppm) | 38 | 6 |
| Cr(ppm) | 8 | Not detected |
| Mn(ppm) | 1369 | 303 |
| Ti(ppm) | 1716 | 0.2 |
Example 2:
a. taking 250g of titanium dioxide byproduct ferrous sulfate, adding 750g of deionized water for dissolution, enabling the mass fraction of ferrous sulfate solution to be about 13.6%, enabling the iron ion content to be about 5%, heating to 60 ℃, stirring to enable solute to be completely dissolved, stopping heating and cooling to 45 ℃, filtering the solution, and carrying out ICP test.
b. Preparing a single high-concentration mixed solution: a 20% strength ammonium carbonate solution and a 10% strength ammonium bifluoride solution. The mixed solution enters the upper stirring paddle 1.1 through the high-concentration mixed solution feeding pipe 5, then comes out from the tail end of the mixed solution and reaches the upper layer of the reaction tank 8, the mixed solution enters the lower stirring paddle 1.2 through the low-concentration mixed solution feeding pipe 7, then comes out from the tail end of the mixed solution and reaches the lower layer of the reaction tank 8, and the adding amount is as follows: 40g of 10% ammonium bifluoride solution, 10% ammonium carbonate solution was added until the pH of the solution was 5.5, the solution was heated to 60℃and continuously stirred laterally at a stirring speed of 60r/min for 20min.
c. 0.15g of flocculant was added to the solution, and the stirring speed was 20r/min, and the stirring time was 10min.
d. Filtering the solution, transferring the solution into a standing tank, and taking the ferrous sulfate solution after impurity removal for ICP test.
The test results are shown in Table 2.
Table 2: iron phosphate detection results:
| sample of | Non-impurity-removed ferrous sulfate solution | Ferrous sulfate solution after impurity removal |
| Fe(％) | 5 | 4.88 |
| Na(ppm) | Not detected | Not detected |
| K(ppm) | 11 | 10 |
| Ca(ppm) | 27 | 25 |
| Mg(ppm) | 5486 | 35 |
| Al(ppm) | 45 | 4 |
| Zn(ppm) | 66 | 15 |
| Ni(ppm) | 37 | 6.8 |
| Cr(ppm) | 5 | Not detected |
| Mn(ppm) | 1412 | 335 |
| Ti(ppm) | 1716 | 1 |
Example 3:
a. taking 250g of titanium dioxide byproduct ferrous sulfate, adding 750g of deionized water for dissolution, enabling the mass fraction of ferrous sulfate solution to be about 13.6%, enabling the iron ion content to be about 5%, heating to 60 ℃, stirring to enable solute to be completely dissolved, stopping heating and cooling to 45 ℃, filtering the solution, and carrying out ICP test.
b. Preparing a multi-gradient concentration mixed solution: mixing solution A:20% ammonium carbonate solution and 10% ammonium bifluoride solution, mixed solution B:10% strength ammonium carbonate solution and 5% strength ammonium bifluoride solution. The mixed solution A and the mixed solution B are directly added to the surface of the ferrous sulfate solution in the reaction tank 8, and the addition amount is as follows: 30g of 10% concentration ammonium bifluoride solution and 20g of 5% concentration ammonium bifluoride solution, adding 10% concentration ammonium carbonate solution until the pH of the solution is 5.5, heating to 60 ℃, continuously and transversely stirring at the stirring speed of 60r/min, and reacting for 20min.
c. 0.15g of flocculant was added to the solution, and the stirring speed was 20r/min, and the stirring time was 10min.
d. Filtering the solution, transferring the solution into a standing tank, and taking the ferrous sulfate solution 1 after impurity removal for ICP test.
e. Repeating the steps a-c, and prolonging the reaction time in the step b to 30min and the stirring time in the step c to 20min.
f. Filtering the solution, transferring the solution into a standing tank, and taking the ferrous sulfate solution 2 after impurity removal for ICP test.
The test results are shown in Table 3.
Table 3 iron phosphate detection results:
example 4:
a. taking 250g of titanium dioxide byproduct ferrous sulfate, adding 750g of deionized water for dissolution, enabling the mass fraction of ferrous sulfate solution to be about 13.6%, enabling the iron ion content to be about 5%, heating to 60 ℃, stirring to enable solute to be completely dissolved, stopping heating and cooling to 45 ℃, filtering the solution, and carrying out ICP test.
b. Preparing a single impurity removing solution: 4g of ammonium bifluoride and 96g of deionized water were added. The single impurity removing solution enters the upper layer stirring paddle 1.1 through the high-concentration mixed solution feeding pipe 5, then comes out from the tail end of the single impurity removing solution and reaches the upper layer of the reaction tank 8, enters the lower layer stirring paddle 1.2 through the low-concentration mixed solution feeding pipe 7, then comes out from the tail end of the single impurity removing solution and reaches the lower layer of the reaction tank 8, is heated to 60 ℃, is stirred at the stirring speed of 60r/min and reacts for 20min.
c. 0.15g of flocculant was added to the solution, and the stirring speed was 20r/min, and the stirring time was 10min.
d. Filtering the solution, transferring the solution into a standing tank, and taking the ferrous sulfate solution after impurity removal for ICP test.
The test results are shown in Table 4.
Table 4: iron phosphate detection results:
| sample of | Non-impurity-removed ferrous sulfate solution | Ferrous sulfate solution after impurity removal |
| Fe(％) | 5 | 4.98 |
| Na(ppm) | Not detected | Not detected |
| K(ppm) | 12 | 11 |
| Ca(ppm) | 30 | 26 |
| Mg(ppm) | 5768 | 86 |
| Al(ppm) | 48 | 15 |
| Zn(ppm) | 58 | 42 |
| Ni(ppm) | 33 | 21 |
| Cr(ppm) | 6 | Not detected |
| Mn(ppm) | 1289 | 862 |
| Ti(ppm) | 1812 | 1252 |
The foregoing embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without collision. The protection scope of the present invention is defined by the claims, and the protection scope includes equivalent alternatives to the technical features of the claims. I.e., equivalent replacement modifications within the scope of this invention are also within the scope of the invention.
Claims (9)
1. A method for removing impurities from titanium dioxide by-product ferrous sulfate is characterized by comprising the following steps: it comprises the following steps:
s1: taking a titanium dioxide byproduct ferrous sulfate with a certain mass, dissolving the titanium dioxide byproduct ferrous sulfate by using deionized water, heating and stirring to dissolve the titanium dioxide byproduct ferrous sulfate so that the ferrous sulfate content in a ferrous sulfate solution is controlled in a certain range, stopping heating when solute is completely dissolved, cooling the solution and then keeping for a certain time, and filtering out insoluble matters to obtain an unremoved ferrous sulfate solution;
s2: adding the ferrous sulfate solution which is not subjected to impurity removal in the step S1 into a reaction tank (8), preparing a mixed solution of ammonium bifluoride and ammonium carbonate with multiple concentration gradients, respectively adding the mixed solution into the reaction tank (8) along with a hollow stirring paddle (1) at the upper layer and the lower layer simultaneously, then adjusting the pH value of the solution to a set value by adding the ammonium carbonate solution, heating, stirring for a period of time, and carrying out hydrolysis sedimentation reaction;
s3: adding a certain amount of flocculating agent into the solution after the reaction for a period of time, and stirring for a period of time to perform flocculation sedimentation;
s4: filtering the solution in the step S3 by using a filter press to obtain a ferrous sulfate solution after impurity removal, transferring the ferrous sulfate solution into a forming tank, standing for a period of time, and measuring the element content of the ferrous sulfate solution;
in the step S2, the mixed solution A of the ammonium bifluoride and the ammonium carbonate with high concentration gradient is prepared and added in the upper layer along with the hollow stirring paddle (1) in the reaction tank (8), and the mixed solution B of the ammonium bifluoride and the ammonium carbonate with low concentration gradient is prepared and added in the lower layer along with the hollow stirring paddle (1) in the reaction tank (8).
2. The method for removing impurities from titanium dioxide by-product ferrous sulfate according to claim 1, which is characterized in that: the titanium dioxide byproduct ferrous sulfate comprises, by mass, 17.0-20.0% of Fe, 0.4-0.8% of Mg, 0.1-0.4% of Ti and 0.1-0.2% of Mn.
3. The method for removing impurities from titanium dioxide by-product ferrous sulfate according to claim 1, which is characterized in that: and S1, heating and dissolving the titanium dioxide byproduct ferrous sulfate at 60 ℃ and cooling at 45 ℃.
4. The method for removing impurities from titanium dioxide by-product ferrous sulfate according to claim 1, which is characterized in that: and S1, controlling the mass percentage of ferrous sulfate in the ferrous sulfate solution in the step S1 to be 12-15%.
5. The method for removing impurities from titanium dioxide by-product ferrous sulfate according to claim 1, which is characterized in that: wherein the mixed solution A is prepared from an ammonium carbonate solution with the mass concentration of 20% and an ammonium bifluoride solution with the mass concentration of 10%, and the mixed solution B is prepared from an ammonium carbonate solution with the mass concentration of 10% and an ammonium bifluoride solution with the mass concentration of 5%; the mass of the finally added ammonium bifluoride is 1.5-2% of the mass of the ferrous sulfate solid serving as the by-product of the titanium dioxide treatment.
6. The method for removing impurities from ferrous sulfate as a titanium white byproduct according to claim 1 or 5, wherein the method comprises the following steps: in the step S2, the pH value of the solution is adjusted to 5-5.5 by adding ammonium carbonate solution with the mass concentration of 10%, then the heating temperature is 60 ℃, the stirring speed is 60r/min, and the stirring time is 20min.
7. The method for removing impurities from titanium dioxide by-product ferrous sulfate according to claim 1, which is characterized in that: in the S2 step, the stirring paddle (1) comprises an upper stirring paddle (1.1) and a lower stirring paddle (1.2), the upper stirring paddle (1.1) and the lower stirring paddle (1.2) are of a hollow pipeline structure which is horizontally arranged, the tail end of the pipeline is open, the head end of the pipeline is communicated with a stirring shaft (2) which is vertically arranged, the stirring shaft (2) is of a hollow pipeline structure, a separation sheet (3) is arranged in the middle of the stirring shaft, the top of the stirring shaft (2) is communicated with a high-concentration mixed solution feeding pipe (5) through an upper rotary joint (4), the bottom of the stirring shaft (2) is communicated with a low-concentration mixed solution feeding pipe (7) through a lower rotary joint (6), the upper side of the stirring shaft (2) is arranged at the top of a reaction tank (8) through a bearing, a first gear (9) is sleeved at the upper end of the stirring shaft (2), the first gear (9) is meshed with a second gear (10), and the second gear (10) is arranged on an output shaft of a servo motor (11). In the feeding process, the mixed solution A enters the upper stirring paddle (1.1) through the high-concentration mixed solution feeding pipe (5), then comes out of the tail end of the mixed solution A and reaches the upper layer of the reaction tank (8), and the mixed solution B enters the lower stirring paddle (1.2) through the low-concentration mixed solution feeding pipe (7) and then comes out of the tail end of the mixed solution B and reaches the lower layer of the reaction tank (8).
8. The method for removing impurities from titanium dioxide by-product ferrous sulfate according to claim 1, which is characterized in that: and S3, the flocculant is cationic polyacrylamide, the amount of the flocculant added is six parts per million of the mass of the titanium dioxide byproduct ferrous sulfate in the step S1, the stirring speed is 20r/min, and the stirring time is 10-30min.
9. The method for removing impurities from titanium dioxide by-product ferrous sulfate according to claim 1, which is characterized in that: and S4, the filter press is a plate-and-frame filter press.
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| CN101607741A (en) * | 2008-06-19 | 2009-12-23 | 张晓东 | Utilize byproduct ferrous sulfate of titanium dioxide to prepare the method for red iron oxide |
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| CN101607741A (en) * | 2008-06-19 | 2009-12-23 | 张晓东 | Utilize byproduct ferrous sulfate of titanium dioxide to prepare the method for red iron oxide |
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| CN108046337A (en) * | 2018-02-11 | 2018-05-18 | 绵阳天明新能源科技有限公司 | A kind of method of purification of byproduct ferrous sulfate of titanium dioxide |
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