CN114162875B - Preparation method and preparation device of ferrous sulfate solution for ferric oxide pigment and ferric oxide pigment - Google Patents
Preparation method and preparation device of ferrous sulfate solution for ferric oxide pigment and ferric oxide pigment Download PDFInfo
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- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 104
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 103
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 103
- 239000000049 pigment Substances 0.000 title claims abstract description 44
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 55
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims abstract description 53
- 235000010215 titanium dioxide Nutrition 0.000 claims abstract description 52
- 239000006227 byproduct Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- -1 hydrogen ions Chemical class 0.000 claims abstract description 41
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 238000005189 flocculation Methods 0.000 claims abstract description 32
- 230000016615 flocculation Effects 0.000 claims abstract description 32
- 238000001556 precipitation Methods 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 239000006228 supernatant Substances 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- 239000002893 slag Substances 0.000 claims abstract description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 238000006073 displacement reaction Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 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 claims description 104
- 238000000034 method Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 5
- 239000012463 white pigment Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 18
- 239000010936 titanium Substances 0.000 abstract description 18
- 229910052719 titanium Inorganic materials 0.000 abstract description 17
- 239000012535 impurity Substances 0.000 abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 95
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 25
- 230000007062 hydrolysis Effects 0.000 description 9
- 239000001034 iron oxide pigment Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000011344 liquid material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D36/00—Filter circuits or combinations of filters with other separating devices
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (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 relates to the technical field of ferric oxide pigment and waste recycling, in particular to a preparation method and a preparation device of ferrous sulfate solution for ferric oxide pigment and ferric oxide pigment. The preparation method comprises the following steps: mixing a titanium white byproduct ferrous sulfate solution with reduced ilmenite, and carrying out a displacement reaction on iron in the reduced ilmenite and hydrogen ions in the ferrous sulfate solution to carry out a hydrolysis reaction on titanic acyl ions and aluminum ions in the ferrous sulfate solution; after the reaction is finished, standing and separating the mixed material to obtain supernatant and slag, mixing the supernatant with a flocculant solution for flocculation precipitation, carrying out solid-liquid separation to obtain ferrous sulfate solution for ferric oxide pigment, and carrying out solid-liquid separation to the slag to obtain the synthetic rutile. The reduced ilmenite is adopted to adjust the pH, so that iron in the reduced ilmenite can react with acid, the pH value of the mixed material is improved, impurities such as titanium and aluminum are removed, the alkali consumption can be reduced, the cost is reduced, and the synthetic rutile is obtained.
Description
Technical Field
The invention relates to the technical field of ferric oxide pigment and waste recycling, in particular to a preparation method and a preparation device of ferrous sulfate solution for ferric oxide pigment and ferric oxide pigment.
Background
In recent years, the demand of iron oxide red in China is continuously increased, the annual growth rate is up to 107%, and the annual growth rate is far higher than 36.6% of that of the whole iron oxide pigment, so that the iron pigment is an iron pigment which is inferior to iron black and iron yellow.
The titanium white pigment produced by the sulfuric acid method is prepared by taking ilmenite (FeTiO 3) as a raw material, decomposing the ore with sulfuric acid, dissolving titanium and iron into sulfate, crystallizing and separating out the iron in the form of ferrous sulfate (FeSO 4·7H2 O), and separating the iron from titanium liquid, thereby becoming a main byproduct for producing titanium white by the method. Ferrous sulfate is also called copperas, and is a solid waste in the production of titanium dioxide by a sulfuric acid method. 1t of titanium dioxide is produced, and 3 to 3.2t of ferrous sulfate heptahydrate is produced. Ferrous sulfate has low value, but if the ferrous sulfate is used as a raw material for producing iron oxide pigments, resources can be effectively utilized, environmental pollution can be reduced, and production cost of iron oxide red can be reduced. If the titanium white byproduct ferrous sulfate is used as a raw material to synthesize the ferric oxide pigment, the cost can be further saved, and the waste of resources is avoided.
The titanium white byproduct ferrous sulfate contains various impurities such as Ti, mn, mg, A and the like besides about 95 percent of ferrous salt. The impurities are mixed in the pigment finished product, which can influence the color light and the performance of the pigment, especially the influence of Ti and A1 is obvious.
After the titanium white byproduct ferrous sulfate is dissolved in water, the pH value is lower, generally about 0.5, which is not beneficial to the removal of titanium by water. In the prior art, the pH value of the ferrous sulfate solution is often adjusted by adding NaOH. However, naOH is costly and is disadvantageous in terms of reducing the cost of the iron oxide pigment.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a method for preparing a ferrous sulfate solution for iron oxide pigment, which not only can raise the pH value of a mixed material after the replacement reaction of iron in reduced ilmenite and acid by adopting reduced ilmenite to adjust the pH of a titanium white byproduct ferrous sulfate solution, thereby promoting the hydrolysis of aluminum ions and titanic acid ions (TiO 2+) in the mixed material to remove impurities such as titanium, aluminum, etc., but also can reduce the alkali consumption and reduce the cost by adopting reduced ilmenite instead of the traditional sodium hydroxide. In addition, iron in the reduced ilmenite is removed by reaction with hydrogen ions, and synthetic rutile can be obtained.
The second object of the present invention is to provide a device for preparing ferrous sulfate solution for ferric oxide pigment, which has the advantages of simple structure, convenient operation, cost saving, etc.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
The invention provides a preparation method of ferrous sulfate solution for ferric oxide pigment, which comprises the following steps:
(a) Mixing the titanium white byproduct ferrous sulfate solution with reduced ilmenite, performing displacement reaction on iron in the reduced ilmenite and hydrogen ions in the ferrous sulfate solution, and performing hydrolysis reaction on titanic acyl ions and aluminum ions in the ferrous sulfate solution;
(b) Standing and separating the mixed materials after the displacement reaction and the hydrolysis reaction are completed to obtain supernatant and slag respectively, mixing the supernatant with a flocculant solution for flocculation precipitation, carrying out solid-liquid separation to obtain ferrous sulfate solution for the ferric oxide pigment, and carrying out solid-liquid separation to the slag to obtain the synthetic rutile;
the titanium white byproduct ferrous sulfate solution is obtained by dissolving a byproduct ferrous sulfate heptahydrate crystal in the process of producing titanium white pigment by a sulfuric acid method;
the cations in the titanium white byproduct ferrous sulfate solution comprise titanic acid ions, aluminum ions, ferrous ions and hydrogen ions.
The reduced ilmenite is obtained by high-temperature reduction of ilmenite, and comprises TiO 2 and metallic Fe as main components.
The titanium white byproduct ferrous sulfate is a byproduct ferrous sulfate heptahydrate crystal in the process of producing titanium white pigment by a sulfuric acid method, and the titanium white byproduct ferrous sulfate solution is obtained after the byproduct ferrous sulfate heptahydrate crystal is dissolved in water.
The pH value of the titanium white byproduct ferrous sulfate solution is lower, generally about 0.5, which is unfavorable for removing titanium by water. Therefore, the invention improves the pH value of the mixed material by adding the reduced ilmenite, wherein iron can be subjected to displacement reaction with hydrogen ions in the titanium white byproduct ferrous sulfate solution, promotes the hydrolysis of aluminum ions and titanic acyl ions (TiO 2+) in the mixed material, and further removes titanium and aluminum impurities. And the reduced ilmenite is adopted to replace sodium hydroxide to adjust the pH value, so that the alkali consumption can be reduced, and the cost is reduced.
In addition, iron in the reduced ilmenite is removed by reaction with hydrogen ions, and synthetic rutile may be obtained for use in the production of downstream products.
The reaction principle of the preparation method of ferrous sulfate solution for ferric oxide pigment provided by the invention is as follows:
In the step (a), the iron in the reduced ilmenite and hydrogen ions in the ferrous sulfate solution undergo a displacement reaction, and simultaneously titanic acid ions and aluminum ions in the ferrous sulfate solution undergo a hydrolysis reaction:
Fe+2H+＝Fe2++H2↑；
TiO2++3H2O＝Ti(OH)4+2H+；
Al3++3H2O＝Al(OH)3+3H+。
iron in the reduced ilmenite can react with hydrogen ions in the titanium white byproduct ferrous sulfate solution, so that the pH value of the solution is improved, and the hydrolysis of titanium and aluminum ions in the solution is promoted; meanwhile, iron can continue to react with hydrogen ions generated after the hydrolysis of titanium and aluminum, so that the hydrolysis of titanium and aluminum ions is further promoted, and titanium and aluminum impurities in the solution are better reduced.
And after the displacement reaction and the hydrolysis reaction are completed, sequentially standing and separating the mixed materials to obtain supernatant and slag. Because of the relatively high density of reduced ilmenite, the reduced ilmenite in the mixture will precipitate to the bottom after a period of standing. At this time, the supernatant is first withdrawn, and then the remaining slag (a part of the liquid contained in the slag) is discharged, thereby completing the separation of the supernatant and the slag.
The particles after the hydrolysis of the titanic acid ions and the aluminum ions are suspended in the supernatant, so that the supernatant is mixed with a flocculating agent solution for flocculation precipitation, the hydrolyzed particles can be settled, and then the ferrous sulfate solution for the ferric oxide pigment is obtained through solid-liquid separation.
And simultaneously, carrying out solid-liquid separation on the slag obtained by the separation, wherein the main component of the slag is reduced ilmenite after reaction, and most of iron in the reduced ilmenite is removed, thus obtaining the synthetic rutile.
In addition, the ferrous sulfate solution for the ferric oxide pigment provided by the invention has low impurity content, and particularly titanium and aluminum which have great influence on the pigment are removed in a large amount, so that the chromatic light and the performance of the ferric oxide pigment can be improved.
Preferably, in the step (a), the molar ratio of the iron element in the reduced ilmenite to the hydrogen ion in the titanium white byproduct ferrous sulfate solution is 1.1-1.5 (1.2, 1.3 or 1.4 may be selected): 2. i.e. a slight excess of iron in the reduced ilmenite.
Preferably, in the step (a), the mass fraction of the iron element in the titanium white byproduct ferrous sulfate solution is 6% -8%, including but not limited to any one of the point values of 6.5%, 7%, 7.5% or a range value between any two.
After the above molar ratio and mass fraction are adopted, the pH value of the mixed material can be increased to be more than 3, so that the hydrolysis of aluminum sulfate and titanyl sulfate serving as impurities in the mixed material can be promoted.
In some embodiments of the invention, since iron in the reduced ilmenite is excessive during the reaction, the slag after the primary reaction may be left in the reaction apparatus for recycling. This also allows a further reduction of the iron content in the synthetic rutile.
In some embodiments of the invention, the slag separated in step (b) contains a portion of the liquid material, so that the liquid material obtained after the solid-liquid separation of the slag may be sent to the flocculation precipitation device for further recovery of ferrous sulfate solution.
Preferably, in the step (a), the pH value of the titanium white byproduct ferrous sulfate solution is 0-1.5.
Preferably, in step (a), the temperature of the mixture is 80-95 ℃; including but not limited to any one of the point values or range values between any two of 82 ℃, 85 ℃, 88 ℃, 90 ℃, 93 ℃.
Preferably, in step (a), the total time of the reaction is 20 to 40min, including but not limited to a point value of any one of 25min, 30min, 35min or a range value between any two.
Preferably, in step (b), the flocculant solution has a volume of 0.1% to 0.3% of the supernatant volume; including but not limited to a point value of any one of 0.13%, 0.15%, 0.18%, 0.2%, 0.23%, 0.25%, 0.28%, or a range value between any two.
Preferably, in the step (b), the mass fraction of the flocculant solution is 0.05% -0.15%; including but not limited to a point value of any one of 0.06%, 0.08%, 0.1%, 0.12%, 0.14%, or a range value therebetween.
Preferably, in step (b), the flocculation precipitation time is 3-5 hours, including but not limited to a point value of any one of 3.5 hours, 4 hours, 4.5 hours or a range value between any two.
In some specific embodiments of the invention, the flocculant comprises polyacrylamide and/or modified polyacrylamide.
Polyacrylamide is a linear high molecular polymer, and is a hard glassy solid at normal temperature, and the products include glue solution, latex, white powder particles, translucent beads, flakes and the like. The thermal stability is good. Can be dissolved in water in any proportion, and the aqueous solution is uniform and transparent liquid.
In some specific embodiments of the invention, the solid-liquid separation process comprises pressure filtration and/or belt filtration.
In some specific embodiments of the present invention, in the step (b), the standing time is 10-30 min, and may be 15min, 20min or 25min.
The invention also provides a preparation device of the ferrous sulfate solution for the ferric oxide pigment, which is suitable for the preparation method of the ferrous sulfate solution for the ferric oxide pigment, and the preparation device is shown in figure 1 and comprises a reaction device, a flocculation precipitation device, a first solid-liquid separation device and a ferrous sulfate solution storage device which are connected in sequence.
The reaction device is also connected with a second solid-liquid separation device.
The second solid-liquid separation device is also connected with an artificial rutile storage device.
The reaction device is used as a reaction container for titanium white byproduct ferrous sulfate solution and reduced ilmenite, the reaction device is stationary for a period of time after the reaction is completed, the supernatant can be separated and obtained, the flocculation precipitation device is used as a container for carrying out flocculation precipitation on the supernatant and flocculant solution, after the flocculation precipitation is completed, the mixed material enters the first solid-liquid separation device for solid-liquid separation, the ferrous sulfate solution for ferric oxide pigment can be obtained, and the ferrous sulfate solution flows into the ferrous sulfate solution storage device for storage.
Meanwhile, the titanium white byproduct ferrous sulfate solution can be separated to obtain slag after the reaction of the titanium white byproduct ferrous sulfate solution and the reduced ilmenite is completed, and the reduced ilmenite can be precipitated to the bottom of the reaction device after standing for a period of time due to high density of the reduced ilmenite. Therefore, the supernatant liquid in the reaction apparatus may be withdrawn first, and then the remaining slag (a part of the liquid contained in the slag) may be discharged, thereby completing the separation of the supernatant liquid and the slag.
After the slag is obtained, the slag is subjected to solid-liquid separation, so that the synthetic rutile (the synthetic rutile refers to a titanium-rich raw material which is produced by separating most of iron components in ilmenite by a chemical processing method and has the same components and structural properties as natural rutile, is a high-quality substitute of the natural rutile, and can be used for producing titanium dioxide by a chlorination process and titanium tetrachloride). The synthetic rutile is placed in the synthetic rutile storage device.
Preferably, a first stirring device is further arranged in the reaction device.
The first stirring device can uniformly mix the titanium white byproduct ferrous sulfate solution and the reduced ilmenite, thereby being beneficial to the full reaction.
Preferably, the top end of the reaction device is provided with a titanium white byproduct ferrous sulfate feed inlet, a water inlet and a reduced ilmenite feed inlet.
Before the reaction, adding the raw materials into a reaction device, wherein titanium white byproduct ferrous sulfate is added from a titanium white byproduct ferrous sulfate feed port, water is added from a water inlet port, and the two substances are mixed to obtain titanium white byproduct ferrous sulfate solution; and reduced ilmenite is added from the reduced ilmenite feed inlet.
Preferably, the top end of the reaction device is also provided with a steam inlet.
The steam inlet is used for introducing steam, so that the temperature of the mixed material is raised, and the hydrolysis of aluminum ions and titanic acid ions (TiO 2+) in the mixed material is promoted.
Preferably, the preparation device further comprises a flocculant solution feed port, wherein the flocculant solution feed port is arranged at the top end of the flocculation precipitation device, and/or the flocculant solution feed port is arranged between the reaction device and the flocculation precipitation device.
The flocculant solution feeding port is used for adding flocculant solution.
If the flocculant solution feeding port is arranged between the reaction device and the flocculation precipitation device, as shown in fig. 1, the flocculant solution and the supernatant can be uniformly mixed in the conveying process, so that the subsequent flocculation precipitation is facilitated.
If the flocculant solution feeding port is arranged at the top end of the flocculation precipitation device, a second stirring device is arranged in the flocculation precipitation device, as shown in fig. 2, so that the flocculant solution and the supernatant are uniformly mixed.
Preferably, a drying device is further arranged between the second solid-liquid separation device and the synthetic rutile storage.
The drying device is used for drying the synthetic rutile.
Preferably, a liquid outlet is further formed in the bottom end of the second solid-liquid separation device, a liquid inlet is further formed in the bottom end of the flocculation precipitation device, and the liquid outlet is connected with the liquid inlet.
The liquid material obtained after the second solid-liquid separation device performs solid-liquid separation can be conveyed to the flocculation precipitation device so as to further recover ferrous sulfate solution.
The invention also provides an iron oxide pigment, which is mainly prepared from the ferrous sulfate solution prepared by the preparation method of the ferrous sulfate solution for the iron oxide pigment or the ferrous sulfate solution prepared by the preparation device of the ferrous sulfate solution for the iron oxide pigment.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the ferrous sulfate solution for the ferric oxide pigment, the reduced ilmenite is added, and iron in the reduced ilmenite can be subjected to displacement reaction with hydrogen ions in the titanium white byproduct ferrous sulfate solution, so that the pH of a mixed material is improved, hydrolysis of aluminum ions and titanic acyl ions (TiO 2+) in the mixed material is promoted, titanium and aluminum impurities are removed, and the color light and performance of the ferric oxide pigment can be improved. And the reduced ilmenite is adopted to replace sodium hydroxide to adjust the pH value, so that the alkali consumption can be reduced, and the cost can be reduced.
(2) The preparation method of ferrous sulfate solution for ferric oxide pigment provided by the invention can be used for regulating the pH value by utilizing reduced ilmenite and simultaneously removing iron in the reduced ilmenite to obtain synthetic rutile, so that the preparation method is further used for producing downstream products.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a device for preparing a ferrous sulfate solution for ferric oxide pigments according to the present invention;
Fig. 2 is another schematic structural diagram of a preparation apparatus of ferrous sulfate solution for ferric oxide pigment provided by the invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The titanium white byproduct ferrous sulfate described in each of the following examples and comparative examples of the present invention is a ferrous sulfate heptahydrate crystal as a byproduct in the production process of titanium white pigment by a sulfuric acid process.
FIG. 1 is a schematic diagram of a device for preparing a ferrous sulfate solution for ferric oxide pigments according to the present invention; fig. 2 is another schematic structural diagram of a preparation apparatus of ferrous sulfate solution for ferric oxide pigment provided by the invention.
Example 1
The preparation device of ferrous sulfate solution for ferric oxide pigment provided in this embodiment is shown in fig. 1, and includes a reaction device, a flocculation precipitation device, a first solid-liquid separation device and a ferrous sulfate solution storage device, which are connected in sequence.
The reaction device is also connected with a second solid-liquid separation device; the second solid-liquid separation device is also connected with an artificial rutile storage device.
The preparation device further comprises a flocculant solution feeding port, and the flocculant solution feeding port is arranged between the reaction device and the flocculation precipitation device.
And a drying device is arranged between the second solid-liquid separation device and the artificial rutile storage device.
A first stirring device is also arranged in the reaction device; the top end of the reaction device is provided with a titanium white byproduct ferrous sulfate feed inlet, a water inlet and a reduced ilmenite feed inlet; the top end of the reaction device is also provided with a steam inlet.
The bottom of the second solid-liquid separation device is also provided with a liquid outlet, the bottom of the flocculation precipitation device is also provided with a liquid inlet, and the liquid outlet is connected with the liquid inlet.
Example 2
In this example, the preparation device of example 1 is used to prepare a ferrous sulfate solution for ferric oxide pigment, and the preparation method of the ferrous sulfate solution for ferric oxide pigment provided in this example specifically includes the following steps:
(1) Adding titanium white byproduct ferrous sulfate and water into a reaction device, and starting a first stirring device to stir to obtain titanium white byproduct ferrous sulfate solution with the mass fraction of iron element of 6% and the pH value of 1; then, introducing steam into the mixture to raise the temperature to 80 ℃ (and keeping the temperature in the processes of displacement reaction and hydrolysis reaction to be 80 ℃), and adding reduced ilmenite into the mixture to ensure that the molar ratio of iron element in the reduced ilmenite to hydrogen ions in the titanium white byproduct ferrous sulfate solution is 1.1:2, carrying out displacement reaction and hydrolysis reaction, stopping stirring after 40min of reaction, and standing for 10min;
(2) Separating the mixture after standing in the step (1), pumping supernatant into a flocculation sedimentation device, discharging the rest slag (a part of liquid is contained in the slag) into a second solid-liquid separation device (a belt filter) for water washing and solid-liquid separation, conveying the liquid material after solid-liquid separation into the flocculation sedimentation device, simultaneously adding a flocculating agent (polyacrylamide) with the mass fraction of 0.05% and the volume of 0.1% of the supernatant into the flocculation sedimentation device for flocculation sedimentation, conveying the supernatant into the first solid-liquid separation device (a filter press) for filter pressing after 5 hours, and pumping into a ferrous sulfate solution storage device to obtain ferrous sulfate solution for ferric oxide pigment after impurity removal;
(3) And (3) conveying the solid material obtained by the solid-liquid separation of the second solid-liquid separation device (belt filter) in the step (2) to a drying device (rotary kiln) for drying, and conveying the solid material to a synthetic rutile storage device to obtain the synthetic rutile.
Example 3
The preparation method of the ferrous sulfate solution for ferric oxide pigment provided in this example is basically the same as that of example 2, except that:
In the step (1), the molar ratio of the iron element in the reduced ilmenite to the hydrogen ions in the titanium white byproduct ferrous sulfate solution is 1.5:2; the mass fraction of iron element in the titanium white byproduct ferrous sulfate solution is 8%, and the pH value is 0.5;
In the step (2), the mass fraction of the flocculant added is 0.15%, and the expected volume is 0.3% of the volume of the supernatant; the flocculation and precipitation time is 3 hours.
Example 4
The preparation method of the ferrous sulfate solution for ferric oxide pigment provided in this example is basically the same as that of example 2, except that:
In the step (1), the molar ratio of the iron element in the reduced ilmenite to the hydrogen ions in the titanium white byproduct ferrous sulfate solution is 1.2:2; the mass fraction of iron element in the titanium white byproduct ferrous sulfate solution is 7%, and the pH value is 0.8; the temperature of the displacement reaction and the hydrolysis reaction was 85℃and the reaction time was 30min.
In the step (2), the mass fraction of the flocculant added is 0.1%, and the volume of the flocculant is 0.2% of the volume of the supernatant fluid; the flocculation and precipitation time is 4 hours.
Comparative example 1
The preparation method of the ferrous sulfate solution for iron oxide pigment provided in this comparative example is substantially the same as in example 2, except that: in step (1), the reduced ilmenite was replaced with 3% by mass of sodium hydroxide solution in an amount to maintain the same pH as the mixture of example 2, and the titanium white by-product ferrous sulfate used in this comparative example was the same batch as in example 2.
Experimental example 1
The iron oxide pigments prepared in example 2, example 3, example 4 and comparative example 1 were subjected to elemental content analysis (elemental aluminum and elemental titanium) using a ferrous sulfate solution and a titanium white byproduct ferrous sulfate solution before reaction, and the results are shown in table 1 below.
TABLE 1 contents of aluminum element and titanium element in each group of solutions
As can be seen from Table 1, the reduction of ilmenite was used to adjust the pH of the ferrous sulfate solution, so that the content of aluminum element could be reduced to 20ppm or less, and the content of titanium element could be reduced to 10ppm or less. And the effect of removing impurities in example 2 is not much different from the comparison of the result of adjusting the pH with sodium hydroxide (i.e., comparative example 1), i.e., reduced ilmenite can replace the conventional sodium hydroxide to adjust the pH so that most of the titanic acid ions and aluminum ions in the ferrous sulfate solution complete the hydrolysis reaction. Therefore, the reduced ilmenite is adopted to replace the traditional sodium hydroxide, so that the alkali consumption can be reduced, and the cost can be reduced; and simultaneously, the impurities of titanium and aluminum can be removed.
The main components of the synthetic rutile prepared in example 2, example 3 and example 4 were simultaneously analyzed for content, and the results are shown in table 2 below.
TABLE 2 major composition of synthetic rutile
As can be seen from the data in table 2, the pH adjustment using reduced ilmenite enabled satisfactory synthetic rutile products.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (16)
1. The preparation method of ferrous sulfate solution for ferric oxide pigment is characterized by comprising the following steps:
(a) Mixing the titanium white byproduct ferrous sulfate solution with reduced ilmenite, performing displacement reaction on iron in the reduced ilmenite and hydrogen ions in the ferrous sulfate solution, and performing hydrolysis reaction on titanic acyl ions and aluminum ions in the ferrous sulfate solution;
(b) Standing and separating the mixed materials after the displacement reaction and the hydrolysis reaction are completed to obtain supernatant and slag respectively, mixing the supernatant with a flocculant solution for flocculation precipitation, carrying out solid-liquid separation to obtain ferrous sulfate solution for the ferric oxide pigment, and carrying out solid-liquid separation to the slag to obtain the synthetic rutile;
the titanium white byproduct ferrous sulfate solution is obtained by dissolving a byproduct ferrous sulfate heptahydrate crystal in the process of producing titanium white pigment by a sulfuric acid method;
the cations in the titanium white byproduct ferrous sulfate solution comprise titanic acid ions, aluminum ions, ferrous ions and hydrogen ions.
2. The method according to claim 1, wherein in the step (a), a molar ratio of the iron element in the reduced ilmenite to the hydrogen ion in the titanium white byproduct ferrous sulfate solution is 1.1 to 1.5:2.
3. The preparation method of claim 1, wherein in the step (a), the mass fraction of iron element in the titanium white byproduct ferrous sulfate solution is 6% -8%.
4. The method according to claim 1, wherein in the step (a), the pH of the titanium white byproduct ferrous sulfate solution is 0 to 1.5.
5. The method according to claim 1, wherein in the step (a), the temperature of the mixture is 80 to 95 ℃.
6. The method according to claim 1, wherein in the step (a), the total reaction time is 20 to 40 minutes.
7. The method according to claim 1, wherein in the step (b), the volume of the flocculant solution is 0.1% -0.3% of the volume of the supernatant.
8. The preparation method according to claim 1, wherein in the step (b), the mass fraction of the flocculant solution is 0.05% -0.15%.
9. The method according to claim 1, wherein in the step (b), the flocculation and precipitation time is 3 to 5 hours.
10. The preparation device of ferrous sulfate solution for ferric oxide pigment is characterized by being suitable for the preparation method of ferrous sulfate solution for ferric oxide pigment according to any one of claims 1-9, wherein the preparation device comprises a reaction device, a flocculation precipitation device, a first solid-liquid separation device and a ferrous sulfate solution storage device which are connected in sequence;
The reaction device is also connected with a second solid-liquid separation device;
The second solid-liquid separation device is also connected with an artificial rutile storage device.
11. The apparatus according to claim 10, wherein a first stirring device is further provided in the reaction apparatus.
12. The preparation device according to claim 10, wherein the top end of the reaction device is provided with a titanium white byproduct ferrous sulfate feed port, a water inlet port and a reduced ilmenite feed port.
13. The apparatus according to claim 10, wherein the top end of the reaction apparatus is further provided with a steam inlet.
14. The apparatus of claim 10, further comprising a flocculant solution feed port disposed at a top end of the flocculation precipitation device and/or disposed between the reaction device and the flocculation precipitation device.
15. The apparatus according to claim 10, wherein a drying device is further provided between the second solid-liquid separation device and the synthetic rutile storage.
16. The apparatus according to claim 10, wherein the bottom end of the second solid-liquid separation apparatus is further provided with a liquid outlet, the bottom end of the flocculation precipitation apparatus is further provided with a liquid inlet, and the liquid outlet is connected with the liquid inlet.
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