CN111470531A - Rutile type chemical fiber titanium dioxide, preparation method and application - Google Patents
Rutile type chemical fiber titanium dioxide, preparation method and application Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 59
- 239000000835 fiber Substances 0.000 title claims abstract description 37
- 239000000126 substance Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 20
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 12
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000013078 crystal Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000413 hydrolysate Substances 0.000 claims description 3
- 239000013067 intermediate product Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 29
- 239000000049 pigment Substances 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 235000010215 titanium dioxide Nutrition 0.000 description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 238000007551 Shore hardness test Methods 0.000 description 1
- 229910010416 TiO(OH)2 Inorganic materials 0.000 description 1
- 229910010270 TiOCl2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
- C01G23/0538—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts in the presence of seeds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/04—Pigments
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/21—Attrition-index or crushing strength of granulates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses rutile chemical fiber grade titanium dioxide, a preparation method and application, and relates to the technical field of pigment preparation. Adding a small amount of stannic oxide into the titanium oxychloride for hydrolysis, wherein the stannic chloride is used as a promoter of rutile titanium dioxide, and can be more thoroughly oriented to rutile metatitanic acid (TiO (OH))2) The method may be carried out by allowing metatitanic acid to grow and set to rutile type titanium dioxide at a lower temperature in the subsequent calcination. The rutile titanium dioxide used as the delustering agent in chemical fibers can be prepared by the method, the particle size distribution of the rutile chemical fiber titanium dioxide prepared by the method is uniform, the requirement of the hardness of the anatase chemical fiber special titanium dioxide is met, and the pigment performance is between rutile and anatase.
Description
Technical Field
The invention relates to the technical field of pigment preparation, in particular to rutile chemical fiber-grade titanium dioxide, a preparation method and application.
Background
At present, the common industrialized production methods of titanium dioxide comprise a sulfuric acid method and a chlorination method. The sulfuric acid method is characterized in that titanium-containing minerals are subjected to acidolysis by sulfuric acid to obtain titanyl sulfate solution, hydrated titanium dioxide precipitate is obtained through purification and hydrolysis, and then the hydrated titanium dioxide precipitate enters a brick kiln to be roasted to produce a titanium dioxide pigment product, the non-continuous production process is a non-continuous production process, the process flow is complex, about 20 steps are required, a large number of operation steps are required for crystal form conversion, more waste is discharged, and a large amount of energy is consumed in the adopted incineration process. The chlorination process is to react ilmenite, high titanium slag, artificial rutile, natural rutile, etc. with chlorine to produce titanium tetrachloride, and to produce titanium dioxide through rectification, purification, gas phase oxidation, fast cooling and gas-solid separation. The chlorination process has high requirements on raw materials, equipment corrosion resistance and great technical difficulty, and can only prepare high-hardness rutile titanium dioxide generally, thereby limiting the application range of the rutile titanium dioxide in chemical fiber, food and other industries.
Titanium dioxide is mainly used as a delustering agent in chemical fibers, and because commercially available rutile titanium dioxide has high hardness and is easy to abrade spinneret holes and a filament cutter, anatase titanium dioxide is generally selected as the delustering agent in the chemical fibers. Generally, chemical fiber grade titanium dioxide has strict requirements on particle size distribution, and the requirement that more than 90% of titanium dioxide has particle size smaller than 1um and does not contain coarse particles more than 5um as far as possible. However, the existing sulfuric acid process is difficult to achieve uniform particle size distribution, and because of the existence of a large amount of small particles and ultra-large particles, particle sintering is easily caused at a high calcination temperature; in addition, because of cost limitation, the prior anatase titanium dioxide is almost not subjected to a wet grinding process, and the conventional Raymond mill is difficult to meet the requirements of chemical fiber titanium dioxide. At present, in order to reduce the sintering phenomenon, potassium salt, phosphate and the like are usually added for salt treatment before the calcining process, however, the salt inevitably affects another important index of the chemical fiber titanium dioxide: dispersibility in water and glycol.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide rutile chemical fiber grade titanium dioxide, a preparation method and application to solve the problems.
The invention is realized by the following steps:
a process for preparing rutile-type chemical-fibre titanium white includes such steps as preparing crystal seeds from the premixed liquid, mixing with the rest of premixed liquid, hydrolysis reaction, calcining for dewatering, and growing particles.
The invention provides a preparation method of rutile type chemical fiber titanium dioxide, which can be used as a delustering agent in chemical fibers.
The titanium dioxide prepared by the preparation method of the rutile chemical fiber titanium dioxide provided by the invention has good dispersibility in water and glycol.
The inventor finds that the tin tetroxide can be used as an accelerant of rutile type titanium dioxide, and can promote the hydrolysis reaction of titanium oxychloride to rutile type metatitanic acid (TiO (OH))2) The subsequent calcination can also be promoted to make the metatitanic acid grow and shape towards the rutile type titanium dioxide at lower temperature.
The hydrolysis reaction equation of titanium oxychloride is as follows: TiOCl2+2H2O＝TiO(OH)2+2HCl。
The equation for the calcination reaction of metatitanic acid is as follows: TiO (OH)2＝TiO2+H2O。
The preparation method provided by the invention is environment-friendly and pollution-free.
In a preferred embodiment of the present invention, the amount of tin tetrachloride added to the pre-mixed solution is 0.05 to 2% of the mass of titanium dioxide in the titanyl dichloride solution.
In the preferred embodiment of the present invention, the concentration of titanium dioxide in the titanyl dichloride solution is 150-300 g/L.
In a preferred embodiment of the invention, the titanium oxychloride solution is derived from an aqueous solution of titanium oxychloride obtained by a hydrochloric acid extraction method or titanium tetrachloride which is an intermediate product of a chlorination process.
The inventor creatively discovers that when the aqueous solution of titanium oxychloride obtained by a hydrochloric acid extraction method or titanium tetrachloride which is an intermediate product of a chlorination method is hydrolyzed by adding tin tetrachloride, rutile-type metatitanic acid is generated, and the particle size of the rutile-type metatitanic acid is larger than that of metatitanic acid hydrolyzed by a sulfuric acid method, sintering is not easy to cause, and the rutile-type metatitanic acid is calcined at a low temperature. The amorphous metatitanic acid particles prepared by sulfuric acid hydrolysis have small and uneven particle size, and fine particles are easy to sinter.
In addition, the existing sulfuric acid hydrolysis for producing metatitanic acid requires addition of an inhibitor to inhibit the formation of rutile titanium dioxide and prevent the particles from being too hard. The present invention can realize the rutile type titanium dioxide with low hardness without adding any inhibitor or surfactant.
In a preferred embodiment of the invention, the tin tetrachloride is mixed with the titanyl dichloride solution to prepare a premixed solution, part of the premixed solution is put into a reaction kettle, water is added, and the mixture is mixed and heated to prepare the seed crystal; and then putting the rest premixed solution into a reaction kettle for reaction.
The crystal seed preparation speed can be greatly improved by adopting a small amount of premix liquid to prepare the crystal seed.
In a preferred embodiment of the present invention, the volume percentage of the selected part of the premix for preparing the seed crystal in the total premix is 0.1-2%.
When the seed crystal is prepared, the addition amount of part of the premix in the above range can rapidly generate the rutile type metatitanic acid.
In the preferred embodiment of the present invention, the volume ratio of the water added to the reaction kettle to the total premix is 1: 3-7.
In a preferred embodiment of the present invention, the volume ratio of the water added to the reaction kettle to the total premix is 1: 4.
In the preferred embodiment of the present invention, the added water is deionized water.
In a preferred embodiment of the present invention, the temperature of the solution in the reaction kettle is 75-105 ℃ when the seed crystal is prepared.
In a preferred embodiment of the present invention, the step of preheating the remaining premixed solution before placing the remaining premixed solution in the reaction kettle further comprises the step of preheating the remaining premixed solution.
The pre-mixed liquid can be preheated to enable the pre-mixed liquid to be instantly hydrolyzed to generate metatitanic acid when being mixed with the seed crystal, so that the situation that irregular seed crystal is automatically hydrolyzed out from titanium oxychloride under the condition of no seed crystal to influence the product quality is avoided.
In the preferred embodiment of the present invention, the temperature of the pre-mixture is pre-heated to 70-75 ℃. And adding the preheated residual premix into the reaction kettle after the reaction kettle turns light blue.
In a preferred embodiment of the application of the present invention, the preheated residual premixed solution is added into the reaction kettle within 20-40min for hydrolysis reaction.
The titanium oxychloride is fully hydrolyzed by mixing at the adding speed, the generation of crystals in the hydrolysis process is ensured, the adding speed is too slow, the generated crystals are few, and the particle size is large; too fast a speed may result in irregular crystals, which may affect the uniformity of the crystals produced.
In a preferred embodiment of the present invention, the temperature of the hydrolysis reaction in the reaction kettle is 85-105 ℃, and the reaction time is 1-5 h.
The hydrolysis can be completely carried out within the above hydrolysis temperature and time.
In the preferred embodiment of the invention, the hydrolyzed product is placed in a muffle furnace to be calcined and dehydrated, and the particles are grown and shaped, wherein the calcination temperature is 500-800 ℃.
In the preferred embodiment of the present invention, the calcination time is 10-50 min.
In a preferred embodiment of the present invention, before calcining the hydrolysate, the method further comprises sequentially filtering, washing and drying the hydrolysate.
The solvent and impurities on the surface of the crystal are removed by filtration and washing. Drying to remove residual water on the crystal surface.
The Shore hardness of the rutile chemical fiber titanium dioxide prepared by the preparation method is lower than 70 and higher than 50.
The produced rutile type titanium dioxide integrates the advantages and the disadvantages of anatase type and rutile type titanium dioxide, meets the hardness requirement of anatase type chemical fiber titanium dioxide, has low impurity content and excellent whiteness and water dispersibility, and has pigment performances such as achromatism and the like between those of the rutile type and the anatase type.
The rutile titanium dioxide prepared by the preparation method is applied to the field of chemical fibers.
The invention has the following beneficial effects:
the invention provides rutile chemical fiber titanium dioxide, a preparation method and application thereof, wherein tin tetroxide is used as an accelerant of rutile titanium dioxide, and can be more thoroughly oriented to rutile metatitanic acid (TiO (OH) in the hydrolysis reaction of titanium oxychloride2) The method may be carried out by allowing metatitanic acid to grow and set to rutile type titanium dioxide at a lower temperature in the subsequent calcination. The crystal seed preparation speed can be greatly improved by adopting part of the premixed liquid to prepare the crystal seed. The rutile type titanium dioxide used as a delustering agent in chemical fibers can be prepared by the method, the particle size distribution of the rutile type chemical fiber titanium dioxide prepared by the method is uniform, the requirement of anatase type chemical fiber titanium dioxide hardness is met, and the pigment performance is between rutile type and anatase type. And the preparation process is simple, the cost is low, the particle sintering phenomenon does not exist, and salt treatment is not needed before calcination.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an XRD spectrum of rutile type chemical fiber titanium dioxide prepared in example 2 of the present invention;
figure 2 is an XRD pattern of kemu R-706.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of rutile chemical fiber titanium dioxide, which comprises the following steps:
s1, firstly, taking TiO provided by Fujian Fushi new material company with finite responsibility21000m L of titanium oxychloride with the concentration of 250 g/L, 1m L SnO2Tin tetrachloride with a concentration of 200 g/L was mixed uniformly (i.e., a premix).
S2, adding 5m L S1 solution into a reaction kettle, then adding 200m L deionized water, mixing and heating to 85 ℃, simultaneously heating the rest S1 solution to 75 ℃, adding the rest S1 solution into the reaction kettle within 30min when the reaction kettle is changed into blue, and maintaining the temperature at 90 ℃ for reaction for 3h to generate rutile metatitanic acid.
S3, washing and drying the rutile type metatitanic acid generated in the S2, putting the rutile type metatitanic acid into a muffle furnace, calcining the rutile type metatitanic acid for 20 minutes at 600 ℃, and dehydrating the metatitanic acid to grow rutile type titanium dioxide.
Example 2
The embodiment provides a preparation method of rutile chemical fiber titanium dioxide, which comprises the following steps:
s1, firstly taking TiO2Titanium oxychloride (1000 m L) with concentration of 200 g/L, SnO2Tin tetrachloride with a concentration of 200 g/L of 2m L was mixed well.
S2, adding 10m L of S1 solution into a reaction kettle, then adding 250m L of deionized water, mixing and heating to 80 ℃, simultaneously preheating the rest S1 solution to 70 ℃, adding the rest S1 solution into the reaction kettle within 25min when the reaction kettle is changed into blue, and maintaining the temperature at 100 ℃ for 2h to react to generate rutile metatitanic acid.
S3, washing and drying the rutile type metatitanic acid generated in the S2, putting the rutile type metatitanic acid into a muffle furnace, calcining the rutile type metatitanic acid for 20 minutes at 700 ℃, and dehydrating the metatitanic acid to grow rutile type titanium dioxide.
Example 3
The embodiment provides a preparation method of rutile chemical fiber titanium dioxide, which comprises the following steps:
s1, firstly taking TiO2150 g/L g/1000 m titanium oxychloride (IBM. TM. L), SnO2The concentration was 200 g/L tin tetrachloride, 2m L.
S2, adding 10m L S1 into a reaction kettle, adding 300m L deionized water, mixing and heating to 95 ℃, simultaneously heating the rest S1 to 75 ℃, adding the rest S1 into the reaction kettle for 20min when the reaction kettle is changed into blue, and reacting for 4h at the temperature of 85 ℃ to generate rutile metatitanic acid.
S3, washing the rutile metatitanic acid generated in the S2, then calcining the washed rutile metatitanic acid in a muffle furnace at 750 ℃ for 10 minutes, and dehydrating the metatitanic acid to grow rutile titanium dioxide.
Comparative example 1
This comparative example was substantially the same as example 1 except that: s3, calcining at 800 ℃ for 20 minutes.
Comparative example 2
The process conditions were substantially the same as those of example 2 except that S2. the S1 solution was added to the reaction vessel, and deionized water 250m L was added and heated to 100 ℃ to maintain the reaction at 100 ℃ for 3 hours, and calcination was carried out at 800 ℃ for 10 minutes.
Comparative example 3
The process conditions were substantially the same as in example 1, except that: in the step S1, TiO is firstly taken2Titanium oxychloride with a concentration of 200 g/L of 1000m L and no tin tetrachloride was added to the S1 solution.
Test examples
At present, no standard of chemical fiber titanium dioxide exists in China, and the quality of the titanium dioxide prepared in the examples 1-3 and the comparative examples 1-3 is detected by referring to the standard of the titanium dioxide for chemical fiber in Japanese industrial standard JIS K1409-1994. The results are shown in Table 1.
TABLE 1 test results
The data show that the quality of the titanium dioxide produced by the method is far higher than the standard of the current chemical fiber titanium dioxide, and the performance of the pigment without tin tetrachloride is greatly reduced.
The hardness detection of the titanium dioxide has no clear standard, and the particle size is expressed by further sanding fine zirconium beads at the same time according to the market rutile is difficult to grind compared with anatase, and referring to the grindability experiment method of cement; referring to the shore hardness test method of plastics, titanium dioxide is made into a high-concentration plastic film, the hardness of the plastic film is tested, and the test result is shown in table 2.
Table 2 test results.
The data show that the titanium dioxide composite material obtained by the comparative example has the calcination temperature of 800 ℃, harder titanium dioxide particles and higher calcination strength, and can not meet the use requirements of the chemical fiber industry.
XRD (X-ray diffraction) spectrum analysis is carried out on the titanium dioxide prepared in the embodiment 2 of the invention, and is shown in figure 1, and XRD spectrum analysis of Kemu R-706 titanium dioxide is shown in figure 2. As can be seen from fig. 1 and 2, no impurity peak was observed in the XRD patterns, and the obtained product was a pure product.
The invention provides a preparation method of rutile chemical fiber titanium dioxide. The method comprises the steps of preparing a titanium oxychloride solution, preparing a seed crystal, adding a preheated titanium solution for hydrolysis, washing, drying and calcining to obtain the rutile chemical fiber titanium dioxide.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of rutile type chemical fiber titanium dioxide is characterized by comprising the steps of preparing seed crystals from part of premixed liquid, mixing the seed crystals with the rest of the premixed liquid, carrying out hydrolysis reaction, calcining and dehydrating the hydrolyzed product, and growing particles, wherein the premixed liquid is the premixed liquid of tin tetrachloride and titanium oxychloride solution.
2. The preparation method according to claim 1, wherein the addition amount of the tin tetrachloride in the premix solution is 0.05 to 2 per mill of the mass of the titanium dioxide in the titanyl dichloride solution.
3. The method as claimed in claim 2, wherein the concentration of titanium dioxide in the titanyl dichloride solution is 150-300 g/L.
4. The method according to claim 3, wherein the solution of titanyl dichloride is derived from an aqueous solution of titanyl dichloride obtained by a hydrochloric acid extraction method or titanium tetrachloride which is an intermediate product of a chlorination process.
5. The preparation method according to claim 1, wherein the tin tetrachloride is mixed with the titanyl dichloride solution to prepare a premixed solution, part of the premixed solution is taken out and put into a reaction kettle, water is added, and the seed crystal is prepared by mixing and heating; then putting the rest premixed solution into the reaction kettle for reaction;
preferably, the volume percentage of the part of the premix liquid in the premix liquid for preparing the seed crystal is 0.1-2%;
preferably, the volume ratio of the water added into the reaction kettle to the premixed liquid during the preparation of the seed crystal is 1: 3-7;
preferably, the volume ratio of the water added into the reaction kettle to the premixed liquid is 1:4 when the seed crystal is prepared;
preferably, the temperature of the solution in the reaction kettle is 75-105 ℃ when the seed crystal is prepared.
6. The method of claim 5, wherein the step of placing the remaining premix solution in the reaction vessel further comprises preheating the remaining premix solution;
preferably, the temperature of the remaining premix is preheated to 70-75 ℃;
preferably, the preheated residual premixed solution is added into the reaction kettle within 20-40min for hydrolysis reaction;
preferably, the temperature for hydrolysis reaction in the reaction kettle is 85-105 ℃, and the reaction time is 1-5 h.
7. The preparation method as claimed in claim 1, wherein the hydrolyzed product is placed in a muffle furnace for calcination, dehydration and particle growth, wherein the calcination temperature is 500-800 ℃;
preferably, the calcination time is 10-50 min.
8. The method of claim 7, wherein the step of filtering, washing and drying the hydrolysate before calcining the hydrolysate.
9. The rutile type titanium dioxide prepared by the preparation method of any one of claims 1-8, wherein the Shore hardness of the rutile type chemical fiber titanium dioxide is lower than 70 and higher than 50.
10. Use of the rutile titanium dioxide obtained by the process according to any of claims 1 to 8 or the rutile titanium dioxide according to claim 9 in the field of chemical fibers.
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