CN105315723B - Preparation method of pearlescent pigment coating material - Google Patents
Preparation method of pearlescent pigment coating material Download PDFInfo
- Publication number
- CN105315723B CN105315723B CN201410378297.5A CN201410378297A CN105315723B CN 105315723 B CN105315723 B CN 105315723B CN 201410378297 A CN201410378297 A CN 201410378297A CN 105315723 B CN105315723 B CN 105315723B
- Authority
- CN
- China
- Prior art keywords
- coating
- pearlescent pigment
- tio
- substrate
- film layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
Provides a preparation method of a pearlescent pigment coating material. The method of the invention is that after dissolving the titanic iron ions in the ilmenite by hydrochloric acid, the titanic iron ions are separated and enriched by an iron extractant to obtain a ferric trichloride-enriched solution and a titanium-containing raffinate, the enriched ferric trichloride can be used for iron series pearlescent pigment coating materials, and colored ions such as Mn and V are extracted and removed from the titanium-containing raffinate by a second extractant to obtain a purified titanium solution which is used for preparing the titanium series pearlescent pigment coating materials.
Description
Technical Field
The invention relates to a method for preparing a pearlescent pigment coating material by acidolysis of ilmenite, in particular to a method for separating ilmenite from titanic iron ions in acidolysis solution by hydrochloric acid acidolysis, wherein the separated iron ions are used as the coating material to prepare the pearlescent pigment, and the titanium solution from which the iron ions are separated is used as the coating material to prepare the pearlescent pigment.
Background
The pearlescent pigment is a pigment with pearl luster formed by coating one or more metal oxides on a flaky substrate, and different pearlescent effects can be obtained by different oxides and oxide thicknesses. At present, most of iron pearlescent pigments adopt ferric trichloride as a precursor of coated iron oxide, and most of titanium pearlescent pigments adopt titanium tetrachloride as a precursor of coated titanium dioxide.
Ilmenite is an oxide ore of titanium and iron, the main ore from which titanium is refined. At present, the method for preparing titanium tetrachloride or titanyl sulfate mainly adopts a chlorination method or a sulfuric acid method, and then the titanium tetrachloride or titanyl sulfate is obtained by rectifying and removing impurities. The chlorination process includes compounding high titanium slag and petroleum coke in certain proportion, crushing, introducing chlorine gas to react to produce titanium tetrachloride gas, condensing to obtain liquefied titanium tetrachloride liquid, filtering and distilling to obtain titanium tetrachloride product. Sulfuric acid is used to infiltrate ore, producing a large amount of waste acid and ferrous sulfate.
At present, there are 2 methods for researching the dissolution of ilmenite by hydrochloric acid, one is as a previous step of a sulfuric acid method, under the conditions of high temperature and low acid ore ratio, impurities in ilmenite are dissolved away, titanium is dissolved and then precipitated in the form of metatitanic acid, and the titanium is used as a raw material for the next step of sulfuric acid dissolution, such as patents CN 1766137a, CN 101935063a, CN 102602991a, CN102616842A and the like; the other method is to directly carry out acid hydrolysis on the ore by hydrochloric acid and then extract and separate titanium chloride, such as US3236596, US 426989, US 6500396B1, US 6375923 and the like. These are used directly to produce synthetic rutile, rather than pearlescent pigment coatings.
Disclosure of Invention
The invention aims to provide a preparation method of a pearlescent pigment coating material. The idea of the invention is that after dissolving the ferrotitanium ions in the ilmenite by hydrochloric acid, separating and enriching the ferrotitanium ions by an extractant, the enriched ferric trichloride can be used for pearlescent pigment coating materials of iron series, titanium in raffinate is extracted by the extractant to the colored ions such as Mn, V and the like in the raffinate, and the titanium solution is purified. Because the titanium series pearlescent pigments adopt titanium chloride acyl with the pH value of the coating between 1.2 and 3.0, under the condition, other ions such as alkali metal ions, alkaline earth metal ions and the like in the solution can not form coating precipitation, thereby not influencing the quality of the titanium series pearlescent pigments.
According to a first embodiment of the present invention there is provided a process for the production of iron systems from ilmeniteA process for preparing pearlescent pigments and titanium-based pearlescent pigments, or, alternatively, a pigment composition comprising iron (Fe) trioxide from ilmenite is provided2O3) Coating or titanium dioxide (TiO)2) Coating or Fe2O3/TiO2A method of coating a pearlescent pigment, the method comprising the steps of:
(1) adding hydrochloric acid and ilmenite into a reaction kettle according to a certain acid/ore mass ratio, heating to an elevated temperature T1 under stirring, reacting at a constant temperature T1 for a period of time, wherein an oxidant is added in the reaction process, cooling the reaction mixture after the reaction is finished, and then performing pressure filtration to obtain a filtrate, namely a hydrochloric acid solution containing ilmenite ions;
(2) adding the solution obtained in the step (1) into an iron extractor, performing multi-stage extraction (such as 3, 4 or 5 stages) by using an iron extractant, combining extracts of all stages serving as organic phases to obtain an iron-rich extract, namely an organic phase A1, and obtaining an aqueous phase which is a titanium-containing raffinate without iron ions after the multi-stage extraction, namely an aqueous phase B1;
(3) adding the extract A1 rich in iron into an iron stripping device, back-extracting iron ions by using an iron stripping agent to obtain an organic phase A2 and a raffinate B2 serving as an aqueous phase containing ferric chloride, pickling the obtained organic phase A2, using the pickled organic phase A2 as the iron stripping agent or returning the organic phase A2 into the iron stripping agent, and extracting the raffinate B2 by using the iron stripping agent again to obtain an iron-containing extract A3 and an aqueous phase B3 serving as organic phases, wherein the organic phase A3 is back-extracted by using the iron stripping agent to obtain the organic phase A4 and a pure ferric trichloride aqueous solution I; preferably, the iron content of the aqueous solution I is in the range of 80-400g/L, preferably in the range of 100-350g/L, more preferably in the range of 120-300g/L, more preferably in the range of 140-250g/L, such as 150g/L, 160g/L or 180 g/L; typically, prior to use, the aqueous solution I may be further concentrated or diluted to a selected concentration;
(4) adding titanium-containing raffinate B1 without iron ions into an impurity removal extractor, and removing colored ions such as manganese and vanadium ions by using an impurity removal extracting agent in a multi-step impurity removal manner to obtain enriched and purified dichlorotitanyl solution II; preferably, the Ti content of the aqueous solution II is in the range of 60 to 300g/L, more preferably in the range of 80 to 250g/L, more preferably in the range of 90 to 200g/L, such as 100g/L, 120g/L or 140 g/L; typically, prior to use, the aqueous solution II may be further concentrated or diluted to a selected concentration; and
(5) a step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 5.1) coating with Fe2O3Film layer: coating Fe on the flaky substrate raw material (or called first-grade flaky substrate or original flaky substrate) by using the ferric trichloride aqueous solution I obtained in the step (3)2O3Film layer of obtained Fe2O3Coated iron-based pearlescent pigment' base material + Fe2O3", i.e., the pearlescent pigment (PP5a) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP5 a.) it may be used as the starting slurry in the next coating process, or it may be further filtered, dried, and calcined to obtain the finished pearlescent pigment PP5a), and
optional substep 5.2) coating of TiO2Film layer: then, the titanyl dichloride solution II of the above step (4) was used to further coat TiO on the pearlescent pigment (PP5a) prepared above as a secondary flaky substrate2Film layer, thereby obtaining a film having Fe2O3Coating layer and TiO2Coated titanic iron pearlescent pigment' substrate + Fe2O3+TiO2", i.e., pearlescent pigment (PP5ab) (which is in the form of a slurry mixture comprising pearlescent pigment (PP5 ab.) it is further filtered, dried, and calcined to obtain the finished pearlescent pigment PP5 ab); and/or
(6) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 6.1) coating of TiO2Film layer: coating TiO on the sheet-shaped substrate raw material by using the titanium dichloride acyl solution II obtained in the step (4)2Film layer to obtain a film having TiO2Coated titanium pearlescent pigment substrate and TiO2", i.e., pearlescent pigment (PP6a) (which is in the form of a slurry mixture comprising pearlescent pigment (PP6a), which can be used as the starting slurry in the next coating process, or which is further filtered, dried, and calcined to obtain the finished pearlescent pigment PP6a),and
optional substep 6.2) coating with Fe2O3Film layer: then, the above prepared pearlescent pigment (PP6a) as a secondary flaky substrate was further coated with Fe using the above aqueous solution I of ferric trichloride of step (3)2O3Film layer, thereby obtaining a film having TiO2Coating layer and Fe2O3Coated titanium-iron pearlescent pigment' base material + TiO2+Fe2O3", i.e., pearlescent pigment (PP6ab) (which is in the form of a slurry mixture comprising pearlescent pigment (PP6 ab.) it is further filtered, dried, and calcined to obtain the finished pearlescent pigment PP6 ab); and/or
(7) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 7.1) coating of TiO2/Fe2O3Film layer: coating TiO on the sheet-like substrate raw material with a mixture of the aqueous ferric trichloride solution I of the above step (3) and the titanyl dichloride solution II of the above step (4) (for example, in a molar ratio of 0.5 to 1.5:1, preferably 1:1, Ti: Fe)2/Fe2O3Film layer to obtain a film having TiO2/Fe2O3Coated titanium/iron pearlescent pigment substrate and TiO2/Fe2O3", i.e. the pearlescent pigment (PP7a) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP7 a.) it may be used as the starting slurry in the next coating process, or it may be further filtered, dried, and calcined to obtain the finished pearlescent pigment PP7a), and optionally the following two substeps 7.2) and 7.3) (typically both substeps must be employed or employed simultaneously):
substep 7.2) SiO coating2Film layer: then, the pearlescent pigment (PP7a) prepared above as a secondary flaky substrate was further coated with SiO using an aqueous solution of sodium metasilicate2Film layer to obtain the pearlescent pigment' substrate + TiO2/Fe2O3+SiO2", i.e., pearlescent pigment (PP7ab) (which is in the form of a slurry mixture comprising pearlescent pigment (PP7 ab.) it may be used as the starting slurry in the next coating process, or it may be further filtered, dried, and calcinedFiring to obtain the finished pearlescent pigment PP7ab), and
substep 7.3) coating of TiO2/Fe2O3Film layer: the pearlescent pigment (PP7ab) prepared above as a secondary platelet substrate is coated with TiO using a mixture of the aqueous ferric trichloride solution I of the above step (3) and the titanyl dichloride solution II of the above step (4) (for example, in a molar ratio of Ti: Fe of 0.5 to 1.5:1, preferably 1: 1)2/Fe2O3Film layer, obtaining a pearlescent pigment substrate + TiO with three coating layers2/Fe2O3+SiO2+TiO2/Fe2O3", i.e., the pearlescent pigment (PP7abc) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP7 abc.) it is further filtered, dried, and calcined to obtain the finished pearlescent pigment PP7 abc); and/or
(8) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 8.1) coating with Fe2O3Film layer: coating Fe on the flaky substrate raw material by using the ferric trichloride aqueous solution I obtained in the step (3)2O3Film layer of obtained Fe2O3Coated iron-based pearlescent pigment' base material + Fe2O3", i.e., pearlescent pigment (PP8a) (which is in the form of a slurry mixture comprising pearlescent pigment (PP8a), which can be used as the starting slurry in the next coating process, or which is further filtered, dried, and calcined to obtain the finished pearlescent pigment PP8a),
substep 8.2) SiO coating2Film layer: then, the pearlescent pigment (PP8a) prepared above as a secondary flaky substrate was further coated with SiO using an aqueous solution of sodium metasilicate2Film layer to obtain the pearlescent pigment' substrate + Fe2O3+SiO2", i.e., the pearlescent pigment (PP8ab) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP8 ab.) it may be used as the starting slurry in the next coating process, or it may be further filtered, dried, and calcined to obtain the finished pearlescent pigment PP8ab), and
substep 8.3) coating with Fe2O3Film layer: use ofThe ferric trichloride aqueous solution I obtained in the step (3) is coated with Fe on the pearlescent pigment (PP8ab) prepared above as a secondary flaky substrate2O3Film layer, obtaining a pearlescent pigment "substrate + Fe" with three coating layers2O3+SiO2+Fe2O3", i.e., the pearlescent pigment (PP8abc) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP8 abc.) it is further filtered, dried, and calcined to obtain the finished pearlescent pigment PP8 abc); and/or
(9) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 9.1) coating of TiO2Film layer: coating TiO on the sheet-shaped substrate raw material by using the titanium dichloride acyl solution II obtained in the step (4)2Film layer to obtain a film having TiO2Coated titanium pearlescent pigment substrate and TiO2", i.e., the pearlescent pigment (PP9a) (which is in the form of a slurry mixture containing the pearlescent pigment (PP9a),. it may be used as the starting slurry in the next coating process, or it may be further filtered, dried, and calcined to obtain the finished pearlescent pigment PP9a),
substep 9.2) SiO coating2Film layer: then, the pearlescent pigment (PP9a) prepared above as a secondary flaky substrate was further coated with SiO using an aqueous solution of sodium metasilicate2Film layer to obtain the pearlescent pigment' substrate + TiO2+SiO2", i.e., the pearlescent pigment (PP9ab) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP9 ab.) it may be used as the starting slurry in the next coating process, or it may be further filtered, dried, and calcined to obtain the finished pearlescent pigment PP9ab), and
substep 9.3) coating of TiO2Film layer: coating TiO on the pearlescent pigment (PP9ab) prepared above as a secondary flaky substrate using the titanyl dichloride solution II of the above step (4)2Film layer, obtaining a pearlescent pigment substrate + TiO with three coating layers2+SiO2+TiO2", i.e., a pearl pigment (PP9abc) (which is in the form of a slurry mixture containing the pearl pigment (PP9abc), it can be used as a starting slurry in the coating process of the next step,or it is further filtered, dried and calcined to obtain the finished pearlescent pigment PP9 abc); and/or
(10) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 10.1) coating SnO2Film layer: SnO coating of the sheet substrate material with an aqueous solution of tin tetrachloride (e.g. 2-5 wt% concentration, e.g. 2.5 wt.%)2Film layer to obtain a film having SnO2Coated tin-based pearlescent pigment' substrate + SnO2", i.e., the pearlescent pigment (PP10a) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP10a),. it may be used as the starting slurry in the next coating process, or it may be further filtered, dried, and calcined to obtain the finished pearlescent pigment PP10a),
substep 10.2) coating of TiO2Film layer: coating TiO 10a on the pearlescent pigment (PP10a) prepared above as a secondary flaky substrate using the titanyl dichloride solution II of the above step (4)2Film layer to obtain a film having SnO2Coating layer and TiO2Coating tin-titanium pearlescent pigment' substrate + SnO2+TiO2", i.e. the pearlescent pigment (PP10ab) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP10 ab.) it may be used as the starting slurry in the next coating process, or it may be further filtered, dried, and calcined to obtain the finished pearlescent pigment PP10ab), and optionally the following two substeps 10.3) and 10.4) (typically both substeps must be employed or employed simultaneously):
substep 10.3) SiO coating2Film layer: further coating SiO on the pearlescent pigment (PP10ab) prepared above as a secondary flaky substrate with an aqueous solution of sodium metasilicate2Film layer to obtain base material of pearl pigment and SnO2+TiO2+SiO2", i.e., the pearlescent pigment (PP10abc) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP10 abc). The pearlescent pigment can be used as a starting slurry in the next coating process, or it can be further filtered, dried, and calcined to obtain the finished pearlescent pigment PP10abc), and
substep 10.4) coating of TiO2Film layer: using step (4) aboveChlorotitanoyl solution II TiO coating on the pearlescent pigment (PP9abc) prepared above as a Secondary sheet substrate2Film layer to obtain the pearlescent pigment' substrate + SnO with four coating layers2+TiO2+SiO2+TiO2", i.e., the pearlescent pigment (PP10abcd) (which is in the form of a slurry mixture comprising the pearlescent pigment (PP10 abcd.) it is further filtered, dried, and calcined to obtain the finished pearlescent pigment PP10 abcd).
Generally, whether a web stock (or primary web) is used or a secondary web is used, it is preferred that the same or substantially the same process conditions be used in the same type of coating process on the web. For example, a raw sheet material (or primary sheet) is coated with Fe2O3The condition of the film layer and the coating of Fe on the secondary flaky substrate2O3The conditions of the film layers are the same or substantially the same. And so on. The process conditions described herein include: pH, reaction temperature, reaction time, etc.
In the present application, a substrate or a sheet-like substrate means or comprises: a web stock (otherwise known as a primary web), or a secondary web. Wherein, the secondary flaky base material is a product obtained by coating at least one film layer on the primary flaky base material or flaky base material. Although the secondary web has been coated with at least one (e.g., one or two or three) film layer, it may still be further coated as a substrate.
In the present application, the initial solids content of the starting slurry is generally between 3 and 25 wt%, preferably between 4 and 20 wt%, more preferably between 5 and 15 wt%, such as 6, 8, 10 or 12 wt%.
In general, a sheet-like substrate is coated with Fe2O3The process or process conditions of the film layer are as follows: in a starting slurry comprising a platelet substrate (e.g. a primary platelet substrate such as a mill-fractionated mica powder raw material, or a secondary platelet substrate) and water (with an initial solids content of between 3 and 25 wt.%, preferably between 4 and 20 wt.%, more preferably between 5 and 15 wt.%, such as 6, 8, 10 or 12 wt.%), at an elevated temperature (T2) (e.g. at 60-95 deg.C, preferably 65-90 deg.C, further preferably 70-90 deg.C, still further preferably 75-8 deg.C)Temperature of 5 ℃) at a pH value in the range of from 1 to 5, preferably from 2 to 4, at a feed rate (for example, at a feed rate of from 1 to 2mL/min for the total amount of starting paste of from 2000-2500 mL), and at the same time obtaining a reaction comprising a pearlescent pigment "substrate + Fe" by adding an alkali solution to keep the pH value of the reaction mixture constant over a period of time (for example, from 5 to 10 hours) to obtain a pearlescent pigment2O3A slurry mixture of particles (referred to as a slurry). The obtained slurry mixture can be used as the initial slurry for the next coating, or the slurry mixture is filtered, the obtained filter cake is dried and then calcined or baked (for example, at the temperature of 850 ℃ C. 950 ℃ C., such as 900 ℃) for example, the obtained filter cake is dried and then put into a muffle furnace, and the temperature is raised to 850 ℃ C. 950 ℃ C., such as 900 ℃ C., at the temperature raising rate of 8-15 ℃/min (such as 10 ℃/min), and the temperature is kept for 0.5-3 hours (1 hour) for calcination, and then the obtained product is taken out and cooled to room temperature, so as to obtain the final product, namely the red iron-based pearlescent pigment.
Generally, the sheet-like substrate is coated with TiO2The process or process conditions of the film layer are as follows: adding or dropping the titanium dichloride acyl solution II prepared in the above step (4) at a certain feed rate (for example, a feed rate of 1-2mL/min for the total amount of the starting slurry of 2000-2500 mL) at a pH value in the range of 1-4, preferably 1.2-3, more preferably 1.5-2.3 at an elevated temperature (T3) (for example, at a temperature of 60-95 ℃, preferably 65-90 ℃, further preferably 70-90 ℃, still further preferably 75-85 ℃) in a starting slurry (initial solid content of 3-25 wt%, preferably 4-20 wt%, more preferably between 5-15 wt%, such as 6, 8, 10 or 12 wt%) comprising a platelet substrate (for example, a mica powder raw material classified by milling, or a secondary platelet) and water, and simultaneously maintaining the pH value of the reaction mixture constant by adding an alkali solution, after a certain period of time (for example 5-10 hours), a "substrate + TiO" comprising pearlescent pigment is obtained2A slurry mixture of particles (referred to as a slurry). The resulting slurry mixture can be used as the starting slurry for further coating or the slurry mixture can be filtered and the resulting filter cake dried and then calcined or baked (e.g., at 750 ℃ C. and 850 ℃ C., such as 800 ℃ C.)) At the temperature of (1), for example, the obtained filter cake is dried and then placed into a muffle furnace, heated to 750-850 ℃ (e.g. 800 ℃) at a heating rate of 8-15 ℃/min (e.g. 10 ℃/min), and then is subjected to heat preservation for 0.5-3 hours (1 hour) for calcination, and then is taken out and cooled to room temperature, so as to obtain the final product, namely the golden iridescent titanium pearlescent pigment.
For coating substrates or sheet-like substrates with SnO2Process for coating film and coating SiO on substrate or sheet-like substrate2The film layer process can adopt the process commonly used in the prior art. Or coating Fe on the flaky substrate2O3Method for coating film or coating TiO on sheet substrate2The film method is the same or similar, only the aqueous solution of tin tetrachloride or sodium metasilicate is used to replace the aqueous solution of ferric trichloride I or titanium dichloride acyl II. To obtain coated SnO2Slurry mixture or SiO coating of film layer2After the slurry mixture of the membrane layer, the obtained slurry mixture can be used as the initial slurry for the next coating, or alternatively, the slurry mixture is filtered, the obtained filter cake is dried and then calcined or baked (for example, at a temperature of 850 ℃ (such as 800 ℃) or 850-.
When the additional film layer is further coated with the secondary sheet-like base material, the type of the outermost coating layer of the secondary sheet-like base material is different from the type of the additional film layer. For example, when the outermost coating layer of the secondary platelet substrate is TiO2When the coating layer is added, TiO is removed2Other types of coating layers than Fe2O3。
In general, the ilmenite in step (1) is a titanium concentrate, ilmenite, high titanium slag or modified titanium concentrate, preferably a titanium concentrate, ilmenite, high titanium slag or modified titanium concentrate having a titanium dioxide content of 30 to 80% by weight, more preferably 40 to 70% by weight, more preferably 45 to 65% by weight.
In general, the concentration of hydrochloric acid in step (1) is 25 to 45% by weight, preferably 28 to 44% by weight, more preferably 30 to 42% by weight, still more preferably 32 to 40% by weight, still more preferably 33 to 37% by weight.
Preferably, the acid/ore mass ratio in step (1) is 1.5-15:1, preferably 2-12:1, more preferably 3-9:1, still more preferably 4-8:1, still more preferably 5-7: 1.
The reaction temperature T1 in step (1) is, for example, in the range of 30 to 90 ℃, preferably 40 to 80 ℃, and more preferably 50 to 75 ℃.
Preferably, the reaction time in step (1) is 2 to 12 hours, preferably 3 to 11 hours, further preferably 4 to 10 hours, further preferably 5 to 9 hours, further preferably 6 to 8 hours. More preferably, the oxidizing agent is added 0.5 to 1 hour before the end of the reaction of step (1). The oxidant is one or more selected from potassium chlorate, sodium chlorate, hydrogen peroxide, sodium peroxide, potassium peroxide, sodium percarbonate or potassium percarbonate, preferably potassium chlorate and sodium chlorate.
Generally, the iron extractant used in step (2) is one or more selected from tributyl phosphate TBP, di (1-methylheptyl) methylphosphonate P350, methylisobutyl ketone MIBK, trioctylamine TOA, primary secondary amine N1923 (i.e., R1R2CHNH2, R1 or R2 are independently C9-C11 alkyl groups), toluene, isoamyl alcohol, or sulfonated kerosene, preferably one or two of tributyl phosphate TBP, primary secondary amine N1923, trioctylamine TOA, toluene, sulfonated kerosene.
In general, step (2) or step (3) or step (4) is carried out at a temperature of 20 to 60 ℃, preferably 25 to 55 ℃, and more preferably 30 to 50 ℃. The step (5) or (6) is carried out at a temperature (T2 or T3) of 60 to 95 ℃, preferably 65 to 90 ℃, more preferably 70 to 90 ℃, still more preferably 75 to 85 ℃.
The mass ratio of the iron extractant to the titaniferous hydrochloric acid solution in step (2) is generally 1 to 6:1, preferably 1.3 to 5:1, more preferably 1.5 to 4:1, more preferably 1.8 to 3:1, and still more preferably 2 to 2.5: 1.
In step (3), the iron stripping agent is one or two selected from deionized water and dilute acid, preferably 0.5-10 wt%, preferably 1-5 wt% of dilute hydrochloric acid.
Preferably, the mass ratio of the iron stripping agent to the iron-rich extract in step (3) is 3-12:1, preferably 4-10:1, more preferably 5-9:1, and still more preferably 6-8: 1.
Preferably, the impurity-removing extractant in the step (4) is one or more selected from tributyl phosphate (TBP), Trioctylamine (TOA), amyl acetate, bis (2-ethylhexyl) phosphate (P204), toluene, xylene, isoamyl alcohol and sulfonated kerosene. The mass ratio of the impurity-removing extractant to the titanium-containing raffinate free of iron ions in step (4) is generally from 1 to 6:1, preferably from 1.3 to 5:1, more preferably from 1.5 to 4:1, still more preferably from 1.8 to 3:1, and still more preferably from 2 to 2.5: 1. Impurity elements such as manganese and vanadium extracted by the impurity removal extracting agent are conveyed to a manganese and vanadium extraction process.
The alkali in the alkali solution used in the present application is one or more selected from sodium hydroxide, ammonia water, and sodium carbonate.
In general, the flaky substrate raw material (or primary flaky substrate) in said step (5) or (6) may be any flaky substrate for pearlescent pigment, preferably natural mica, synthetic mica, glass flake, flaky alumina, flaky silica and various flaky metals.
According to a second embodiment of the present invention, there are provided various types of pearlescent pigments obtained by the above-mentioned method, which are: substrate + TiO2
Substrate + SnO2+TiO2。
Substrate + SnO2+TiO2+SiO2+TiO2
Substrate + TiO2+Fe2O3
Substrate + TiO2/Fe2O3
Substrate + TiO2/Fe2O3+SiO2+TiO2/Fe2O3
Base material + Fe2O3
Base material + Fe2O3+TiO2
Base material + Fe2O3+SiO2+Fe2O3
Substrate + TiO2+SiO2+TiO2. The substrate as used herein means: a sheet substrate stock or a primary sheet substrate.
The pearlescent pigments obtained in the present invention generally have an average particle size of 90 to 350um, preferably 140-300um, more preferably 180-250 um.
According to a third embodiment of the present invention, there is provided the above flaky substrate/Fe2O3Pearlescent pigment or platelet-shaped substrate/TiO2Use of pearlescent pigments in the field of paints, printing inks, plastics, ceramic materials, leather pigmentation, wallpaper, powder coatings or cosmetics.
The invention successfully prepares the raw materials of ferric trichloride and titanium dichloride acyl which can be used as pearlescent pigment envelopes by taking ilmenite and hydrochloric acid as main starting materials for the first time.
In this application, "optional" means with or without and "optionally" means with or without.
"coating" is used interchangeably with "envelope" or "coating layer" or "film layer" in this application. ' Fe2O3/TiO2The coating layer is made of Fe2O3And TiO2A coating layer formed from the mixture of (1). For example, substrate + TiO2/Fe2O3+SiO2+TiO2/Fe2O3Showing that the substrate is coated with TiO in sequence2/Fe2O3Film layer of SiO2Film layer, and TiO2/Fe2O3And (5) film layer. And so on.
The invention relates to a reaction kettle and an extractor which are common equipment for technicians in the field, and the extraction, the back extraction, the grinding, the pulping, the stirring and the temperature-reducing and pressure-filtering are common technologies for technicians in the field. "optionally" means with or without. Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The technical methods which are not detailed in the text are all the technical methods which are commonly used in the field.
The reagents used in the present invention, such as "hydrochloric acid", "mica", "potassium chlorate", "sodium chlorate", "hydrogen peroxide", "tributyl phosphate TBP", "di (1-methylheptyl) methylphosphonate P350", "methylisobutylketone MIBK", "trioctylamine TOA", "primary secondary amine N1923", "toluene", "isoamyl alcohol", "sulfonated kerosene", "deionized water", "dilute hydrochloric acid", "tributyl phosphate TBP", "trioctylamine TOA", "amyl acetate", "P204 bis (2-ethylhexyl) phosphate", "xylene", "isoamyl alcohol", "sodium hydroxide", "ammonia water" and "sodium carbonate", are all common commercially available materials.
The modified titanium concentrate used in the invention refers to titanium concentrate after oxidizing roasting and reducing roasting. Such as offered by the climbing flower iron and steel company, china.
THE ADVANTAGES OF THE PRESENT INVENTION
1. The invention directly adopts ilmenite to prepare the pearlescent pigment for the first time, reduces a large number of intermediate links such as separation and purification, and reduces the cost by 40 to 50 percent compared with the traditional titanium series or iron series pearlescent pigment.
2. Iron oxides, which have been once used as wastes or low-value products in the extraction process of ilmenite, are also utilized in the present invention to produce high value-added iron-based pearlescent pigments. The iron oxide of 2-3 thousand yuan/ton is changed into high-quality pearlescent pigment of several ten thousand yuan/ton, so that the economic benefit is obviously improved.
3. The requirements on the grade or the content of ilmenite are not high, and the application range is wider.
4. Zero emission can be basically realized in the whole preparation process, and the influence on the environment is reduced.
5. The process is simple and has strong operability.
6. The process of the invention is suitable for large-scale industrial production. The economic and social benefits are very outstanding.
Drawings
FIG. 1 is a production flow diagram of the present process.
Detailed Description
For a further understanding of the present invention, reference will now be made in detail to the following examples, which are included to illustrate, but are not to be construed as limiting the present invention, and it is intended that the description be regarded as illustrative rather than restrictive, and that the features and advantages of the present invention are provided. Any equivalent replacement in the field made in accordance with the present disclosure is within the scope of the present invention.
Example 1
(1) Taking 500g of high titanium slag (the content of titanium dioxide is 38.7wt percent), adding 1500g of concentrated hydrochloric acid with the concentration of 37 percent, stirring, raising the temperature to 60 ℃, reacting for 9 hours, and adding 40g of NaClO3Continuing to react for 1h, stopping reaction, cooling to room temperature, performing filter pressing, and washing filter residues to be neutral; (2) extracting an oil phase and a water phase at 30 ℃ by using TBP/MIBK (wt) ═ 1:1 as an extracting agent and performing 3-level extraction compared with O/A ═ 2:1, wherein the oil phase is an iron extraction phase and the water phase is a titanium-containing raffinate phase; (3) and (3) performing back extraction on the iron extraction phase by using deionized water at a ratio of O/A to 1:10, returning an oil phase extracting agent to an Fe extractor, purifying water phase iron through extraction-back extraction, evaporating partial water, concentrating to ensure that the iron content reaches 160g/L, and preparing the ferric trichloride solution capable of being used as the pearlescent pigment coating.
Example 2
The same process conditions as in example 1 were followed except that titanium concentrate was used instead of the high titanium slag.
Example 3
The same process conditions as in example 1 were followed except that the high titanium slag was replaced by modified titanium concentrate.
Example 4
(1) Taking 400g of titanium concentrate (the content of titanium dioxide is 46.6wt percent), adding 1600g of 35 percent concentrated hydrochloric acid, stirring, raising the temperature to 70 ℃, reacting for 7 hours, adding 50g of KClO3Continuing to react for 1h, stopping reaction, cooling to room temperature, performing filter pressing, and washing filter residues to be neutral; (2) extracting an oil phase and a water phase at a temperature of 30 ℃ by using TBP/toluene (wt) ═ 1:2 as an extracting agent and performing 4-stage extraction compared with O/A ═ 3:1, wherein the oil phase is an iron extraction phase and the water phase is a titanium extraction raffinate phase; (3) back extracting the iron extraction phase with deionized water at a ratio of O/A to 1:10, returning the oil phase extractant to the Fe extractor, and extracting the water phase ironBack extraction is carried out for purification, part of water is evaporated out for concentration, the iron content reaches 160g/L, and ferric trichloride solution is obtained; the titanium raffinate phase reaches an impurity removal extractor, multistage countercurrent extraction V is carried out by using extracting agents TBP/dimethylbenzene of 4:25 and O/A of 2:1, raffinate enters an impurity removal extractor 2, TOA/methylbenzene of 1:9 and O/A of 2:1 are used for extracting Mn, and the raffinate is titanium-rich TiOCl after the extract is subjected to back extraction2The Ti content can reach 100000ppm, and the titanium dichloride acyl solution which can be used as a pearlescent pigment coating is prepared.
Example 5 (micaceous iron)
Weighing 100g of mica with the particle size of 10-60 mu m and the diameter-thickness ratio of more than 50, placing the mica in a 2L beaker, adding 1500mL of deionized water, placing the mica in a water bath kettle, stirring at the speed of 200 plus 300rps, heating to the temperature of 75-85 ℃, adjusting the pH value of the solution to be 3-4, taking the ferric trichloride aqueous solution in the implementation case 1 or 4, dropwise adding the ferric trichloride aqueous solution into the beaker at the speed of 2mL/min, maintaining the pH value of the solution unchanged by using a 30% NaOH solution, reacting for 5-6 hours, filtering, drying a filter cake, placing the dried filter cake in a muffle furnace, heating to 900 ℃ at the heating speed of 10 ℃/min, preserving the temperature for 1 hour, taking out, and cooling to room temperature to obtain the red micaceous iron pearlescent pigment.
Example 6 (mica/iron trioxide/silica/iron trioxide)
Weighing 100g of mica with the particle size of 10-60 mu m and the diameter-thickness ratio of more than 50, placing the mica in a 2L beaker, adding 1500mL of deionized water, placing the mica in a water bath kettle, stirring at the speed of 200-300rps, heating to the temperature of 75-85 ℃, adjusting the pH value of the solution to 3-4, taking the ferric trichloride aqueous solution in the implementation case 1 or 4, dropwise adding the ferric trichloride aqueous solution into the beaker at the speed of 2mL/min, keeping the pH value of the solution unchanged by using a 30% NaOH solution, after reacting for 5-6 hours, increasing the pH value to 8.0 by using a 30% NaOH solution, dropwise adding a 20% sodium metasilicate aqueous solution at the speed of 1.0mL/min, after reacting for 1 hour, adjusting the pH value of the solution to 3-4 by using 1:1 hydrochloric acid, dropwise adding the solution into the beaker at the speed of 2mL/min, keeping the pH value of the solution unchanged by using a 30% NaOH solution, reacting for 5-6 hours, filtering, drying the filter cake, putting the filter cake into a muffle furnace, heating to 900 ℃ at the heating rate of 10 ℃/min, preserving the heat for 1 hour, taking out, and cooling to room temperature to obtain the red micaceous iron pearlescent pigment.
Example 7 (titanium dichloride titanium mica)
Weighing 100g of mica with the particle size of 10-60 mu m and the diameter-thickness ratio of more than or equal to 60, placing the mica in a 5L beaker, adding 2000mL of deionized water, placing the mica in a water bath kettle, stirring the mica at the speed of 200 plus 300rps, heating the mica to the temperature of 60-70 ℃, adjusting the pH value of the solution to 1.2-1.8, adding 100mL of 2.5% tin tetrachloride aqueous solution, maintaining the pH value of the solution unchanged by 30% NaOH solution, completing the addition for half an hour, then heating the solution to the temperature of 75-85 ℃, adjusting the pH value of the solution to 1.5-2.5, taking the titanium chloride acyl solution in the practical example 4, dripping the titanium chloride acyl solution into the beaker at the speed of 1mL/min, maintaining the pH value of the solution unchanged by NaOH solution, reacting the solution for 6-7 hours, filtering, drying a filter cake, placing the filter cake in a muffle furnace, heating the temperature to 800 ℃ at the temperature of 10 ℃/min, keeping the temperature for 1 hour, taking out, thus obtaining the golden iridescent mica titanium pearlescent pigment.
Example 8
Weighing 100g of mica with the particle size of 10-60 mu m and the diameter-thickness ratio of more than or equal to 60, placing the mica in a 5L beaker, adding 2000mL of deionized water, placing the mica in a water bath kettle, stirring at the speed of 200 plus 300rps, heating to the temperature of 60-70 ℃, adjusting the pH value of the solution to be 1.2-1.8, adding 100mL of 2.5% tin tetrachloride aqueous solution, maintaining the pH value of the solution unchanged by 30% NaOH solution, completing the addition for half an hour, then heating to the temperature of 75-85 ℃, adjusting the pH value of the solution to be 1.5-2.5, taking titanium chloride acyl solution in the practical example 4, dropwise adding the titanium chloride acyl solution into the beaker at the speed of 1mL/min, maintaining the pH value of the solution unchanged by NaOH solution, increasing the pH value to 8.0 by 30% NaOH solution after reacting for 6-7 hours, dropwise adding 20% sodium metasilicate aqueous solution at the speed of 1.0mL/min, reacting for 1 hour, regulating the pH value of the solution to be 1.5-2.5 by using hydrochloric acid with the ratio of 1:1, dripping the hydrochloric acid into a beaker at the speed of 1mL/min, maintaining the pH value of the solution unchanged by using NaOH solution, reacting for 6-7 hours, filtering, drying a filter cake, putting the dried filter cake into a muffle furnace, heating to 800 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 1 hour, taking out, and cooling to room temperature to obtain the golden iridescent mica titanium pearlescent pigment.
Example 9
Weighing 100g of mica with the particle size of 10-60 mu m and the diameter-thickness ratio of more than or equal to 60, placing the mica in a 5L beaker, adding 2000mL of deionized water, placing the mica in a water bath kettle, stirring at the speed of 200 plus 300rps, heating to the temperature of 60-70 ℃, adjusting the pH value of the solution to be 1.2-1.8, adding 100mL of 2.5% tin tetrachloride aqueous solution, maintaining the pH value of the solution unchanged by 30% NaOH solution, completing the addition for half an hour, then heating to the temperature of 75-85 ℃, adjusting the pH value of the solution to be 1.5-2.5, taking the titanium chloride acyl solution in the embodiment 4, dropwise adding the titanium chloride acyl solution into the beaker at the speed of 1mL/min, maintaining the pH value of the solution unchanged by NaOH solution, increasing the pH value to be 3-4 by 30% NaOH solution after reacting for 6-7 hours, dropwise adding the titanium chloride acyl solution into the beaker at the speed of 2mL/min, maintaining the pH value of the solution unchanged by 30% NaOH solution, and (3) after 5-6 hours of reaction, filtering, drying the filter cake, putting the filter cake into a muffle furnace, heating to 900 ℃ at the heating rate of 10 ℃/min, preserving the heat for 1 hour, taking out, and cooling to room temperature to obtain the golden pearlescent pigment.
Performance index and optical performance of pearlescent pigment
Table 1 shows the performance index of pearlescent pigment
| Serial number | Particle size (D50 μm) | Density (g/cm3) | Oil absorption (g/100g) | Bulk density (g/cm3) | pH of 10% Wt |
| KC205 | 22.5 | 3.1 | 60.5 | 0.25 | 7.76 |
| Example 7 | 22.1 | 3.2 | 61.2 | 0.27 | 7.8 |
| Example 5 | 22.5 | 3.3 | 62.3 | 0.28 | 7.7 |
| KC500 | 22.3 | 3.2 | 62.7 | 0.27 | 7.6 |
TABLE 2 optical Properties of the pearlescent pigments
Note: KC500 and KC205 are two models of commercially available products from fujian kuncao corporation (china).
Application examples
The pearlescent pigments prepared in the above examples 5 to 9 are used in the fields of applications such as paints, coatings, printing inks, plastics, ceramic materials, leather coloring, wall papers, powder coatings, cosmetics, and the like. For example, the addition of the pearlescent pigments of the invention to paints or coatings enables the production of coatings which are very excellent in hue and luster.
Application example 1: paint spray application as an example:
accurately weigh 4.00 grams of pearlescent pigment (product of one of examples 5 or 6 or 7 or 8 or 9), add 4.0 grams of butyl acetate and 8.0 grams of polyester automotive coating resin, place under a stirrer and stir for 10 minutes, continue to add 84.0 grams of automotive coating resin system and stir for 5 minutes. The viscosity of the coating was adjusted to 14-15 seconds for Ford 4 cup before spraying. And during spraying, the temperature of a spraying room is controlled to be 25 ℃, and the relative humidity is controlled to be 60%. Spraying twice, flashing for 10 minutes, covering with varnish, flashing again, and baking at 140 ℃ for 30 minutes.
Application example 2: taking injection molding applications as an example:
200g of polypropylene (PP) material dried at 105 ℃ is accurately weighed into a plastic sealing bag, 1ml of gloss oil (also called dispersing oil) is added, and then the mixture is shaken to fully mix the gloss oil and the polypropylene material.
Preparation with an analytical balance 4.000 g of the pearlescent powder (product of one of examples 5 or 6 or 7 or 8 or 9) was weighed into a plastic sealed bag, shaken again, and kneaded to disperse the pearlescent powder sufficiently and uniformly in the PP particles.
After the temperature of the charging barrel reaches a set value (usually 180-200 ℃), adding the prepared polypropylene material into a hopper, extruding the original residual material in the charging barrel by using the functions of injecting glue and melting glue until a new material is extruded, wherein the extruded new material has luster, no impurities, no black spots, no scorching and no bubbles; meanwhile, the nozzle is not blocked during glue injection. After the front and the rear plastic sheets are not different, the produced plastic sheets are stable and qualified products, and can enter automatic normal production.
Claims (29)
1. A process for the production of iron (Fe) trioxide from ilmenite2O3) Coating or titanium dioxide (TiO)2) Coating or Fe2O3/TiO2A method of coating a pearlescent pigment, the method comprising the steps of:
(1) adding hydrochloric acid and ilmenite into a reaction kettle according to the acid/ore mass ratio of 3-9:1, heating to an elevated temperature T1 while stirring, and reacting at a constant temperature T1 for a period of time, wherein an oxidant is added in the reaction process, and after the reaction is finished, cooling and then carrying out filter pressing on the reaction mixture to obtain a filtrate, namely a hydrochloric acid solution containing ilmenite ions; wherein the reaction temperature T1 is 30-90 ℃, and the oxidant is one or more selected from potassium chlorate, sodium chlorate, hydrogen peroxide, sodium peroxide, potassium peroxide, sodium percarbonate or potassium percarbonate;
(2) adding the solution obtained in the step (1) into an iron extractor, performing multi-stage extraction by using an iron extractant, combining extracts of all stages serving as organic phases to obtain an iron-rich extract, namely an organic phase A1, and obtaining a titanium-containing raffinate without iron ions, namely an aqueous phase B1, after the multi-stage extraction; wherein the iron extractant is one or more selected from tributyl phosphate TBP, methyl phosphonic acid bis (1-methyl heptyl) ester P350, methyl isobutyl ketone MIBK, trioctylamine TOA, secondary carbon primary amine N1923, toluene, isoamyl alcohol or sulfonated kerosene;
(3) adding the extract A1 rich in iron into an iron stripping device, back-extracting iron ions by using an iron stripping agent to obtain an organic phase A2 and a raffinate B2 serving as an aqueous phase containing ferric chloride, pickling the obtained organic phase A2, using the pickled organic phase A2 as the iron stripping agent or returning the organic phase A2 into the iron stripping agent, and extracting the raffinate B2 by using the iron stripping agent again to obtain an iron-containing extract A3 and an aqueous phase B3 serving as organic phases, wherein the organic phase A3 is back-extracted by using the iron stripping agent to obtain the organic phase A4 and a pure ferric trichloride aqueous solution I; wherein the iron stripping agent is deionized water or 0.5-10 wt% dilute hydrochloric acid;
(4) adding titanium-containing raffinate B1 which does not contain iron ions into an impurity removal extractor, and removing colored ions by using an impurity removal extracting agent in multiple steps to obtain an enriched and purified dichlorotitanyl solution II, wherein the Ti content of the dichlorotitanyl solution II is in the range of 60-300g/L, and the impurity removal extracting agent in the step (4) is one or more selected from tributyl phosphate TBP, trioctylamine TOA, amyl acetate, di (2-ethylhexyl) phosphoric acid P204, toluene, xylene, isoamylol and sulfonated kerosene; and
(5) a step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 5.1) coating with Fe2O3Film layer: coating Fe on the flaky substrate raw material by using the ferric trichloride aqueous solution I obtained in the step (3)2O3Film layer of obtained Fe2O3Coated iron-based pearlescent pigment' base material + Fe2O3", i.e., pearlescent pigment (PP5a), and
optional substep 5.2) coating of TiO2Film layer: then, the titanyl dichloride solution II of the above step (4) was used to further coat TiO on the pearlescent pigment (PP5a) prepared above as a secondary flaky substrate2Film layer, thereby obtaining a film having Fe2O3Coating layer and TiO2Coated titanic iron pearlescent pigment' substrate + Fe2O3+TiO2", i.e., pearlescent pigment (PP5 ab); and/or
(6) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 6.1) coating of TiO2Film layer: coating TiO on the sheet-shaped substrate raw material by using the titanium dichloride acyl solution II obtained in the step (4)2Film layer to obtain a film having TiO2Coated titanium pearlescent pigment substrate and TiO2", i.e., pearlescent pigment (PP6a), and
optional substep 6.2) coating with Fe2O3Film layer: then, the above prepared pearlescent pigment (PP6a) as a secondary flaky substrate was further coated with Fe using the above aqueous solution I of ferric trichloride of step (3)2O3Film layer, thereby obtaining a film having TiO2Coating layer and Fe2O3Coated titanium-iron pearlescent pigment' base material + TiO2+Fe2O3", i.e., pearlescent pigment (PP6 ab); and/or
(7) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 7.1) coating of TiO2/Fe2O3Film layer: using the aqueous solution of ferric trichloride I of the above step (3) and the aboveCoating TiO on the flaky substrate raw material by the mixture of the titanium dichloride acyl solution II in the step (4)2/Fe2O3Film layer to obtain a film having TiO2/Fe2O3Coated titanium/iron pearlescent pigment substrate and TiO2/Fe2O3", i.e. pearlescent pigment (PP7a), and optionally the following two substeps 7.2) and 7.3):
substep 7.2) SiO coating2Film layer: then, the pearlescent pigment (PP7a) prepared above as a secondary flaky substrate was further coated with SiO using an aqueous solution of sodium metasilicate2Film layer to obtain the pearlescent pigment' substrate + TiO2/Fe2O3+SiO2", i.e., pearlescent pigment (PP7ab), and
substep 7.3) coating of TiO2/Fe2O3Film layer: coating TiO on the pearlescent pigment (PP7ab) prepared above as a secondary flaky substrate with a mixture of the aqueous solution I of ferric trichloride obtained in the above step (3) and the titanium dichloride acyl solution II obtained in the above step (4)2/Fe2O3Film layer, obtaining a pearlescent pigment substrate + TiO with three coating layers2/Fe2O3+SiO2+TiO2/Fe2O3", i.e., pearlescent pigment (PP7 abc); and/or
(8) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 8.1) coating with Fe2O3Film layer: coating Fe on the flaky substrate raw material by using the ferric trichloride aqueous solution I obtained in the step (3)2O3Film layer of obtained Fe2O3Coated iron-based pearlescent pigment' base material + Fe2O3", i.e., pearlescent pigment (PP8a),
substep 8.2) SiO coating2Film layer: then, the pearlescent pigment (PP8a) prepared above as a secondary flaky substrate was further coated with SiO using an aqueous solution of sodium metasilicate2Film layer to obtain the pearlescent pigment' substrate + Fe2O3+SiO2", i.e., pearlescent pigment (PP8ab), and
substep 8.3) coating with Fe2O3Film layer: coating Fe on the above-prepared pearlescent pigment (PP8ab) as a secondary flaky substrate with the above-prepared ferric trichloride aqueous solution I of step (3) above2O3Film layer, obtaining a pearlescent pigment "substrate + Fe" with three coating layers2O3+SiO2+Fe2O3", i.e., pearlescent pigment (PP8 abc); and/or
(9) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 9.1) coating of TiO2Film layer: coating TiO on the sheet-shaped substrate raw material by using the titanium dichloride acyl solution II obtained in the step (4)2Film layer to obtain a film having TiO2Coated titanium pearlescent pigment substrate and TiO2", i.e., pearlescent pigment (PP9a),
substep 9.2) SiO coating2Film layer: then, the pearlescent pigment (PP9a) prepared above as a secondary flaky substrate was further coated with SiO using an aqueous solution of sodium metasilicate2Film layer to obtain the pearlescent pigment' substrate + TiO2+SiO2", i.e., pearlescent pigment (PP9ab), and
substep 9.3) coating of TiO2Film layer: coating TiO on the pearlescent pigment (PP9ab) prepared above as a secondary flaky substrate using the titanyl dichloride solution II of the above step (4)2Film layer, obtaining a pearlescent pigment substrate + TiO with three coating layers2+SiO2+TiO2", i.e., pearlescent pigment (PP9 abc); and/or
(10) A step of coating a sheet-like substrate, the coating step comprising the following substeps:
substep 10.1) coating SnO2Film layer: SnO coating on flaky substrate raw material by using stannic chloride aqueous solution2Film layer to obtain a film having SnO2Coated tin-based pearlescent pigment' substrate + SnO2", i.e., pearlescent pigment (PP10a),
substep 10.2) coating of TiO2Film layer: coating TiO 10a on the pearlescent pigment (PP10a) prepared above as a secondary flaky substrate using the titanyl dichloride solution II of the above step (4)2Film layer to obtain a film having SnO2Coating layer and TiO2Coating tin-titanium pearlescent pigment' substrate + SnO2+TiO2", i.e. pearlescent pigment (PP10ab), and optionally the following two substeps 10.3) and 10.4):
substep 10.3) SiO coating2Film layer: further coating SiO on the pearlescent pigment (PP10ab) prepared above as a secondary flaky substrate with an aqueous solution of sodium metasilicate2Film layer to obtain base material of pearl pigment and SnO2+TiO2+SiO2", i.e., a pearlescent pigment (PP10abc), and
substep 10.4) coating of TiO2Film layer: coating TiO 9abc on the pearlescent pigment prepared above as a secondary flaky substrate using the titanyl dichloride solution II of the above step (4)2Film layer to obtain the pearlescent pigment' substrate + SnO with four coating layers2+TiO2+SiO2+TiO2", i.e., pearlescent pigment (PP10 abcd);
wherein the sheet-like substrate is coated with TiO2The process or process conditions of the film layer are as follows: adding or dropping the titanium dichloride acyl solution II prepared in the step (4) at a certain feeding rate in a starting slurry comprising a flaky substrate and water at an elevated temperature (T3) of 60-95 ℃ and a pH value in the range of 1.2-3, and simultaneously reacting for a period of time by adding an alkali solution to keep the pH value of the reaction mixture constant to obtain a substrate + TiO containing pearlescent pigment2The slurry mixture of the particles is used as the initial slurry for the next coating, or the slurry mixture is filtered, the obtained filter cake is dried, then calcined or baked, and cooled to room temperature, and the golden iridescent titanium pearlescent pigment is obtained.
2. The process according to claim 1, wherein in substep 7.1) and substep 7.3), the molar ratio of Ti to Fe in the mixture of the aqueous solution of ferric trichloride I of step (3) above and the solution of titanium dichloride II of step (4) above is 0.5-1.5: 1.
3. The method of claim 1, wherein the platelet substrate is coated with Fe2O3The process or process conditions of the film layer are as follows: adding or dropwise adding the aqueous solution I of ferric trichloride prepared in the step (3) at a certain feeding rate in a starting slurry comprising a flaky substrate and water at an elevated temperature (T2) of 60-95 ℃ and a pH value in the range of 1-5, and simultaneously reacting for a certain period of time by adding an alkali solution to keep the pH value of the reaction mixture constant to obtain a mixture containing pearlescent pigment' substrate + Fe ]2O3The obtained slurry mixture can be used as initial slurry for coating in the next step, or the slurry mixture is filtered, the obtained filter cake is dried, then calcined or baked, and cooled to room temperature, so that the red iron-based pearlescent pigment is obtained.
4. The method of claim 1, wherein the platelet substrate is coated with TiO2In the process or technology of the film layer, the titanium dichloride acyl solution II prepared in the step (4) is added or dripped at a certain feeding rate under the pH value of 1.5-2.3.
5. A process according to claim 3 or 4, wherein the initial solids content of the starting slurry is between 3 and 25 wt%.
6. A process according to claim 3 or 4, wherein the initial solids content of the starting slurry is between 5 and 15 wt%.
7. The process according to claim 1, characterized in that the ilmenite in step (1) is a titanium concentrate, a high titanium slag or a modified titanium concentrate.
8. The process of claim 7, wherein the ilmenite in step (1) is a titanium concentrate, ilmenite, high titanium slag, or modified titanium concentrate having a titanium dioxide content of 30-80 wt%.
9. The process of claim 8, wherein the ilmenite in step (1) is a titanium concentrate, ilmenite, high titanium slag, or modified titanium concentrate having a titanium dioxide content of 45-65 wt%.
10. The process according to claim 1, wherein the concentration of hydrochloric acid in step (1) is 25 to 45% by weight.
11. The process according to claim 1, wherein the concentration of hydrochloric acid in step (1) is 30 to 42 wt.%.
12. The process according to claim 1 or 10, characterized in that the acid/ore mass ratio in step (1) is 5-7: 1.
13. The process according to any one of claims 1 to 4, characterized in that the reaction temperature T1 of step (1) is between 50 and 75 ℃.
14. The process according to any one of claims 1 to 4, wherein the reaction time in step (1) is 2 to 12 hours, and/or wherein the oxidizing agent is added 0.5 to 1 hour before the end of the reaction.
15. The process according to claim 14, wherein the reaction time in step (1) is 5-9 hours, and/or wherein the oxidizing agent is added 0.5-1 hour before the end of the reaction.
16. Process according to any one of claims 1 to 4, characterized in that the oxidants used in step (1) are potassium chlorate and sodium chlorate.
17. The process according to any one of claims 1 to 4, wherein the iron extractant of step (2) is one or two selected from tributyl phosphate (TBP), primary secondary carbon amine N1923, trioctylamine TOA, toluene, sulfonated kerosene.
18. The process according to any one of claims 1 to 4, characterized in that step (2) or step (3) or step (4) is carried out at a temperature of 20-60 ℃; and/or
The step (5) or (6) is carried out at a temperature of 60 to 95 ℃.
19. The process according to any one of claims 1 to 4, characterized in that step (2) or step (3) or step (4) is carried out at a temperature of 30-50 ℃; and/or
The step (5) or (6) is carried out at a temperature of 75 to 85 ℃.
20. A process according to any one of claims 1 to 4 characterised in that the mass ratio of extractant to titaniferous hydrochloric acid solution in step (2) is in the range 1 to 6: 1.
21. A process according to any one of claims 1 to 4 characterised in that the mass ratio of extractant to titaniferous hydrochloric acid solution in step (2) is in the range 2 to 2.5: 1.
22. The process according to any one of claims 1 to 4, characterized in that the mass ratio of the iron stripping agent to the iron-rich extract in step (3) is 3 to 12: 1.
23. The process according to any one of claims 1 to 4, characterized in that the mass ratio of the iron stripping agent to the iron-rich extract in step (3) is 6-8: 1.
24. The process according to any one of claims 1 to 4, wherein the mass ratio of the dedust extractant to the titanium-containing raffinate free of ferric ions in step (4) is 1 to 6: 1.
25. The process according to any one of claims 1 to 4, wherein the mass ratio of the dedust extractant to the titanium-containing raffinate free of ferric ions in step (4) is 2 to 2.5: 1.
26. The method according to any one of claims 1 to 4, wherein the plate-like substrate material is natural mica, synthetic mica, glass flakes, plate-like alumina, plate-like silica or various plate-like metals.
27. The method according to any one of claims 1 to 4, wherein the platelet-shaped substrate material is natural mica or synthetic mica.
28. The method according to claim 1, wherein the Ti content of the titanium dichloride acyl solution II is in the range of 80-250 g/L.
29. The method according to claim 1, wherein the Ti content of the titanium dichloride acyl solution II is in the range of 90-200 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410378297.5A CN105315723B (en) | 2014-08-04 | 2014-08-04 | Preparation method of pearlescent pigment coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410378297.5A CN105315723B (en) | 2014-08-04 | 2014-08-04 | Preparation method of pearlescent pigment coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105315723A CN105315723A (en) | 2016-02-10 |
| CN105315723B true CN105315723B (en) | 2020-04-03 |
Family
ID=55244078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410378297.5A Active CN105315723B (en) | 2014-08-04 | 2014-08-04 | Preparation method of pearlescent pigment coating material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105315723B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705625A (en) * | 2019-02-25 | 2019-05-03 | 华东理工大学 | A kind of preparation method of the red pearlescent pigment of wine |
| CN110358327A (en) * | 2019-07-25 | 2019-10-22 | 汕头市镇发珠光颜料有限公司 | A kind of high-purity red pearl effect pigment and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114949A (en) * | 1994-07-09 | 1996-01-17 | 山东大学 | Preparation method of high-purity micro-fine rutile-type titanium dioxide |
| CN1130200A (en) * | 1995-03-02 | 1996-09-04 | 天津市同生化工厂 | Method for preparing mica titanium perlatolic pigment |
| CN1422309A (en) * | 2000-04-11 | 2003-06-04 | 默克专利股份有限公司 | Transparent medium having angle-selective transmission or reflection properties and/or absorption properties |
| CN1766137A (en) * | 2005-11-11 | 2006-05-03 | 陈泽安 | Hydrochloric acid-extraction method for preparing rutile titanium white |
| CN1803936A (en) * | 2005-12-14 | 2006-07-19 | 林一中 | Multi-layer coated effect interference pigment and preparation method thereof |
| CN101974258A (en) * | 2010-10-14 | 2011-02-16 | 河北欧克精细化工股份有限公司 | Multilayer color change pigment with high saturation and preparation method thereof |
| CN102046551A (en) * | 2008-05-27 | 2011-05-04 | 默克专利股份有限公司 | Glass-ceramic discs for use in pigments |
| CN102602991A (en) * | 2012-03-05 | 2012-07-25 | 四川大学 | Preparation method of pigment-level titanium dioxide powder by cyclic hydrochloric acid micro emulsion method |
| CN102876090A (en) * | 2012-09-29 | 2013-01-16 | 汕头市澄海区镇发珠光颜料有限公司 | Interference-effect enhanced pearlescent pigment preparation method and product thereof |
| CN103382530A (en) * | 2003-11-19 | 2013-11-06 | 加拿大钛有限公司 | Process for the recovery of titanium in mixed chloride media |
| CN103849168A (en) * | 2012-11-29 | 2014-06-11 | 陈浠 | Pearlescent pigment applied as car spray paint and preparation method thereof |
-
2014
- 2014-08-04 CN CN201410378297.5A patent/CN105315723B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114949A (en) * | 1994-07-09 | 1996-01-17 | 山东大学 | Preparation method of high-purity micro-fine rutile-type titanium dioxide |
| CN1130200A (en) * | 1995-03-02 | 1996-09-04 | 天津市同生化工厂 | Method for preparing mica titanium perlatolic pigment |
| CN1422309A (en) * | 2000-04-11 | 2003-06-04 | 默克专利股份有限公司 | Transparent medium having angle-selective transmission or reflection properties and/or absorption properties |
| CN103382530A (en) * | 2003-11-19 | 2013-11-06 | 加拿大钛有限公司 | Process for the recovery of titanium in mixed chloride media |
| CN1766137A (en) * | 2005-11-11 | 2006-05-03 | 陈泽安 | Hydrochloric acid-extraction method for preparing rutile titanium white |
| CN1803936A (en) * | 2005-12-14 | 2006-07-19 | 林一中 | Multi-layer coated effect interference pigment and preparation method thereof |
| CN102046551A (en) * | 2008-05-27 | 2011-05-04 | 默克专利股份有限公司 | Glass-ceramic discs for use in pigments |
| CN101974258A (en) * | 2010-10-14 | 2011-02-16 | 河北欧克精细化工股份有限公司 | Multilayer color change pigment with high saturation and preparation method thereof |
| CN102602991A (en) * | 2012-03-05 | 2012-07-25 | 四川大学 | Preparation method of pigment-level titanium dioxide powder by cyclic hydrochloric acid micro emulsion method |
| CN102876090A (en) * | 2012-09-29 | 2013-01-16 | 汕头市澄海区镇发珠光颜料有限公司 | Interference-effect enhanced pearlescent pigment preparation method and product thereof |
| CN103849168A (en) * | 2012-11-29 | 2014-06-11 | 陈浠 | Pearlescent pigment applied as car spray paint and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105315723A (en) | 2016-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10377639B2 (en) | Preparation method for directly synthesizing titanium dioxide from titanium-rich organic phase prepared from ilmenite | |
| EP3138816B1 (en) | Method for preparing nanometer titanium dioxide | |
| US5630995A (en) | Preparation of anatase titanium dioxide | |
| KR101928089B1 (en) | Method for preparing pearlescent pigments from hydrochloric acid acidolysis solution of ilmenite by co-extraction | |
| CN104530772B (en) | A kind of composite pigment and preparation method thereof | |
| CN105315723B (en) | Preparation method of pearlescent pigment coating material | |
| US20150252448A1 (en) | Production of high-grade synthetic rutile from low-grade titanium-bearing ores | |
| CN103305032B (en) | Iron oxide yellow viscosity reduction method | |
| JP4977967B2 (en) | Iron-based black particle powder, black paint and rubber / resin composition using the iron-based black particle powder | |
| CN104386759A (en) | Production process for preparing iron oxide red employing ferrous sulfate solution | |
| CN103952568B (en) | The method of process titanium-containing blast furnace slag | |
| CN107572584B (en) | A kind of preparation method of titanium dioxide | |
| CN108690377A (en) | A kind of pearlescent pigment and preparation method thereof with thousand pure gold effects | |
| CN105647241A (en) | Preparation method of fluorescent sericite cosmetics | |
| CN104445433A (en) | Production process for preparing iron oxide yellow by using ferrous sulfate solution | |
| CN104830100A (en) | Method for reducing iron oxide yellow viscosity | |
| CN105948133A (en) | {0><}0{>Method for reducing viscosity of iron oxide yellow | |
| CN105080927B (en) | With the method for magnesium sulfate separating calcium from chloride system | |
| CN109054455A (en) | A kind of preparation method for strengthening interference gold bead delustering pigment | |
| CN106280575A (en) | A kind of paint pearlescent pigment and preparation method thereof | |
| CN102390871A (en) | Preparation technology for low water-absorption heavy iron oxide yellow pigment | |
| RU2084402C1 (en) | Method of processing sphene | |
| CN105087948A (en) | Method for recycling aluminum from blast furnace slag through multistage acid leaching | |
| IE20180407U1 (en) | Polyacrylate coating production plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |