CN110040775A - A kind of preparation method of the unformed titanium dioxide of low-sulfur - Google Patents
A kind of preparation method of the unformed titanium dioxide of low-sulfur Download PDFInfo
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- CN110040775A CN110040775A CN201910447114.3A CN201910447114A CN110040775A CN 110040775 A CN110040775 A CN 110040775A CN 201910447114 A CN201910447114 A CN 201910447114A CN 110040775 A CN110040775 A CN 110040775A
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- titanium dioxide
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
- C01P2006/80—Compositional purity
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Abstract
The present invention provides a kind of unformed titanium dioxide process of low-sulfur, and its step are as follows: (1) it is qualified to wash the hydrolysis metatitanic acid obtained in sulfuric acid method titanium pigment technique, and washing terminal is until iron content is lower than 30ppm；(2) basic treatment: being made slurry for the qualified metatitanic acid of washing, and stirring is warming up to 40-75 DEG C, and buck is added to adjust pH, heat preservation a period of time；(3) acidic treatment: dilute hydrochloric acid is added in step (2) metatitanic acid obtained and adjusts pH, heat preservation a period of time；(4) step (3) resulting metatitanic acid is washed, until washing is qualified, washing qualified index is cleaning solution conductivity≤100 μ s/cm；(5) the metatitanic acid low temperature drying that washing is qualified, obtains the unformed titanium dioxide of low-sulfur.The unformed titanium dioxide prepared by the method for the invention remains the specific surface area of metatitanic acid, and activity is strong, and purity is high, can be used for preparing various titanium base materials.
Description
Technical field
The invention belongs to titanium dioxide preparation technical fields, and in particular to a kind of unformed titanium dioxide preparation side of low-sulfur
Method.
Background technique
Recently as the increasing of environment protection treating dynamics, the exploitation of titanium base material is more and more burning hoter, and product is widely used in de-
Nitre catalysis, photocatalysis, sewage treatment, new energy sources for automobile, salt lake mention lithium etc..The exploitation of titanium base material, primary raw material are exactly
Unformed hydrolysis metatitanic acid.In sulfuric acid method titanium pigment production, titanium sulfate liquid is made through acidolysis containing perovskite powder, after purification concentration
Qualified titanium liquid, which is hydrolyzed, is made metatitanic acid, and the metatitanic acid after washing is qualified is calcined to obtain after salt treatment into rotary kiln falls kiln product,
Fall kiln product can be obtained anatase titanium dioxide finished product after crushing packing, and rutile-type must be crushed, classification, post-processing is sanded after ability
Obtain finished product.Typical sulfuric acid method titanium pigment production technology is the following steps are included: (1) uses ilmenite concentrate or acid-dissolved titanium slag and sulfuric acid
Acidolysis reaction is carried out, titanyl sulfate solution is obtained；(2) hydrolysing titanyl sulfate solution obtains thick metatitanic acid slurry；(3) to thick inclined titanium
Wintercherry material is bleached, is washed, and obtains washing qualified metatitanic acid；(4) it washes qualified metatitanic acid and carries out salt treatment, must pre-process partially
Metatitanic acid；(5) calcine: pretreatment metatitanic acid is sent into rotary kiln and calcines to obtain titanium dioxide base-material；(6) titanium dioxide base-material work after post treatment
Titanium dioxide product is made in sequence.Metatitanic acid after washing is qualified, the impurity based on iron are removed completely substantially, reach ppm grades, but still
Adsorb a certain amount of SO4 2-, usually 6~10%.The presence of sulphur has a great impact to the manufacture of titanium base material, especially forges
A large amount of SO to be discharged when burning2、SO3Gas, with a large amount of alkaline water spray could qualified discharge, while during acid waste water wants
It could be discharged with processing, generate waste residue again in this way, acid waste gas is also very serious to corrosive pipeline.
Two patents of publication number CN106830064A and CN106698508A are the methods about metatitanic acid wet desulphurization,
It is neutralized, then filter cake after neutralization is further washed, to be taken off by the alkaline reagent metatitanic acid qualified to washing
Sulphur metatitanic acid.But the pH value of the qualified metatitanic acid of washing is directly adjusted to 3~4 with alkaline solution by it, by the technological means,
Most of absorption sulfuric acid can only be neutralized, a part combines sulfuric acid that can not remove.It is mentioned in 108408770 A of publication number CN and uses ammonia
Sulfuric acid in water and in metatitanic acid, but its filter cake is not washed, and a large amount of ammonium sulfate are contained in filter cake, and one side sulfate radical is not complete
Removing can generate ammonia and discharged nitrous oxides into atmosphere when on the other hand calcining, cause environmental pollution.Publication number CN
Metatitanic acid pH value range 6~8, which is adjusted, using alkaline reagent in 106986380 A carrys out neutralisation of sulphuric acid.On the one hand within the scope of this pH
Metatitanic acid washing is difficult, and under another aspect alkaline state, metatitanic acid can adsorb a part of cation impurity, using the product to rear
Continuous production has adverse effect.
Summary of the invention
It is scientific and reasonable, simple and easy, raw the object of the present invention is to provide a kind of unformed titanium dioxide process of low-sulfur
It produces low in cost.
The unformed titanium dioxide process of a kind of low-sulfur of the present invention, its step are as follows:
(1) it is qualified to wash the hydrolysis metatitanic acid obtained in sulfuric acid method titanium pigment technique, and washing terminal is until iron content
Lower than 30ppm；
(2) basic treatment: slurry is made in the qualified metatitanic acid of washing, stirring is warming up to 40-75 DEG C, buck is added to adjust
PH, heat preservation a period of time；
(3) acidic treatment: dilute hydrochloric acid is added in step (2) metatitanic acid obtained and adjusts pH, heat preservation a period of time；
(4) step (3) resulting metatitanic acid is washed, until washing is qualified, washing qualified index is cleaning solution conductance
Rate≤100 μ s/cm；
(5) the metatitanic acid low temperature drying that washing is qualified, obtains the unformed titanium dioxide of low-sulfur.
Step (2) buck is potassium hydroxide, sodium hydroxide, ammonium hydroxide, alkali carbonate, any in alkali metal hydrogencarbonate
Alkaline aqueous solution.
Step (2) pH control range 7~10, preferably 9-10.
Step (2) soaking time 0.5~2 hour.
Step (3) pH control range 4~7, preferably 5-6.
Step (2) step (3) soaking time 0.5~2 hour, step (2) is warming up to 40-55 DEG C.
Step (4) is washed to Liu Han Liang≤0.05%.
100~500 DEG C of temperature controlling range of step (5).
Step (3) pH is 5.5.
Compared with prior art, the present invention having the following beneficial effects:
Scientific and reasonable, simple and easy, low production cost of the invention.The present invention is by carrying out at alkalinity acidity metatitanic acid
Reason, does not change original production procedure, greatly reduces the sulfur content in metatitanic acid, and reducing calcination temperature in calcining makes metatitanic acid
The not easy-sintering in calcination process can discharge after the simple water spray of tail gas.
Metatitanic acid pH is adjusted to certain alkaline range by using alkaline matter by step (2) of the present invention, can be neutralized
All absorption sulfuric acid is simultaneously removed in conjunction with sulfuric acid.During adding alkali in a certain range by temperature control, energy can both be reduced
Consumption can also be improved the efficiency that removing combines sulphur；PH is adjusted to faintly acid, especially pH and is adjusted to 5-6 by step (3), on the one hand anti-
Stop cation to be adsorbed by metatitanic acid, on the other hand metatitanic acid is easier to wash under this pH range.It makes by the method for the invention
Standby unformed titanium dioxide remains the specific surface area of metatitanic acid, and activity is strong, and purity is high, can be used for preparing various titanium-baseds
Material.
Detailed description of the invention
Fig. 1 is that unformed titanium dioxide prepared by the present invention and rutile titanium dioxide compare XRD spectrum
Specific embodiment
The invention will be further described with reference to embodiments.Embodiment carries out the total sulfur in the metatitanic acid after drying
Measurement.
Embodiment 1
Qualified metatitanic acid 100g, slurry concentration 320g/L are washed in water intaking, and stirring is warming up to 60 DEG C, 10% hydrogen-oxygen is added
Change sodium solution to pH8, keeps the temperature 1h, 10% hydrochloric acid tune pH6 is added, keep the temperature 0.5h, washed, sulphur is surveyed in 100 DEG C of metatitanic acid drying
Content 0.05%.
Embodiment 2
Qualified metatitanic acid 100g, slurry concentration 320g/L are washed in water intaking, and stirring is warming up to 60 DEG C, 10% hydrogen-oxygen is added
Change potassium solution to pH9, keeps the temperature 1h, 10% hydrochloric acid tune pH5 is added, keep the temperature 0.5h, washed, sulphur is surveyed in 100 DEG C of metatitanic acid drying
Content 0.04%.
Embodiment 3
Qualified metatitanic acid 100g, slurry concentration 300g/L are washed in water intaking, and stirring is warming up to 55 DEG C, 10% hydrogen-oxygen is added
Change potassium solution to pH9, keeps the temperature 2h, 6% hydrochloric acid tune pH5 is added, keep the temperature 1h, washed, 200 DEG C of metatitanic acid drying are surveyed sulphur and contained
Amount 0.01%.
Embodiment 4
Qualified metatitanic acid 100g, slurry concentration 400g/L are washed in water intaking, and stirring is warming up to 40 DEG C, 10% hydrogen-oxygen is added
Change potassium solution to pH10, keeps the temperature 0.5h, 5% hydrochloric acid tune pH6 is added, keep the temperature 2h, washed, sulphur is surveyed in 500 DEG C of metatitanic acid drying
Content 0.01%.
Comparative example 1
The metatitanic acid 100g for taking factory A washing qualified, 100 DEG C of metatitanic acid drying, surveys sulfur content 2.8%
Comparative example 2
The metatitanic acid 100g for taking factory B washing qualified, 100 DEG C of metatitanic acid drying, surveys sulfur content 2.5%
Subordinate list
Sulfur content (%) after 100 DEG C of different metatitanic acids drying
| S content | |
| Embodiment 1 | 0.04 |
| Embodiment 2 | 0.05 |
| Embodiment 3 | 0.01 |
| Embodiment 4 | 0.01 |
| Comparative example 1 | 2.8 |
| Comparative example 2 | 2.5 |
Claims (11)
1. a kind of preparation method of the unformed titanium dioxide of low-sulfur, it is characterised in that steps are as follows:
(1) it is qualified to wash the hydrolysis metatitanic acid obtained in sulfuric acid method titanium pigment technique, and washing terminal is lower than for iron content
30ppm；
(2) basic treatment: being made slurry for the qualified metatitanic acid of washing, and stirring is warming up to 40-75 DEG C, and buck is added to adjust pH, protects
Warm a period of time；
(3) acidic treatment: dilute hydrochloric acid is added in step (2) metatitanic acid obtained and adjusts pH, heat preservation a period of time；
(4) step (3) resulting metatitanic acid is washed, until washing is qualified, wash qualified index be cleaning solution conductivity≤
100μs/cm；
(5) the metatitanic acid low temperature drying that washing is qualified, obtains the unformed titanium dioxide of low-sulfur.
2. a kind of preparation method of the unformed titanium dioxide of low-sulfur according to claim 1, it is characterised in that step (2) alkali
Water is potassium hydroxide, sodium hydroxide, ammonium hydroxide, alkali carbonate, alkaline aqueous solution any in alkali metal hydrogencarbonate.
3. a kind of preparation method of the unformed titanium dioxide of low-sulfur according to claim 1, it is characterised in that step (2) pH
Control range 7~10.
4. a kind of preparation method of the unformed titanium dioxide of low-sulfur according to claim 1, it is characterised in that step (2) is protected
0.5~2 hour warm time.
5. a kind of preparation method of the unformed titanium dioxide of low-sulfur according to claim 1, it is characterised in that step (3) pH
Control range 4~7.
6. a kind of preparation method of the unformed titanium dioxide of low-sulfur according to claim 1, it is characterised in that step (3) is protected
0.5~2 hour warm time.
7. a kind of preparation method of the unformed titanium dioxide of low-sulfur according to claim 1, it is characterised in that step (4) water
It is washed till Liu Han Liang≤0.05%.
8. a kind of preparation method of the unformed titanium dioxide of low-sulfur according to claim 1, it is characterised in that step (5) temperature
100~500 DEG C of control range of degree.
9. a kind of preparation method of the unformed titanium dioxide of low-sulfur according to claim 3, it is characterised in that step (2) pH
Control range 9~10.
10. according to claim 1 or a kind of preparation method of the unformed titanium dioxide of low-sulfur described in 9, it is characterised in that step
(2) it is warming up to 40-55 DEG C.
11. a kind of preparation method of the unformed titanium dioxide of low-sulfur according to claim 5, it is characterised in that step (3)
PH control range 5~6.
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| CN201910440984 | 2019-05-24 | ||
| CN2019104409848 | 2019-05-24 |
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Citations (10)
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|---|---|---|---|---|
| US5527469A (en) * | 1995-06-12 | 1996-06-18 | Lawhorne; Earl R. | Method for the preparation of desulfurized titanium oxide hydrolysate of high purity |
| WO1999043616A1 (en) * | 1998-02-24 | 1999-09-02 | Rotem Amfert Negev Ltd. | A modified titanium dioxide and a method for its preparation |
| CN1539745A (en) * | 2003-10-28 | 2004-10-27 | 南宁一泓环境工程有限公司 | Filterpressing, washing, cleansing processes for manufacturing hydration titania |
| CN101092245A (en) * | 2007-07-09 | 2007-12-26 | 朱贤荣 | Methods for preparing and using crystal seeds of rutile in high activity |
| CN103030175A (en) * | 2012-12-29 | 2013-04-10 | 上海安赐机械设备有限公司 | Device and method applied to metatitanic acid washing room |
| CN103531363A (en) * | 2013-10-24 | 2014-01-22 | 攀枝花学院 | Preparation method of slurry for photoanode of nano TiO2 membrane of dye-sensitized solar cell |
| CN104828861A (en) * | 2015-05-13 | 2015-08-12 | 攀枝花学院 | Method for producing pigment titanium dioxide by performing industrial metatitanic acid size grading |
| CN204873875U (en) * | 2015-01-09 | 2015-12-16 | 上海安赐机械设备有限公司 | Green sulfate process titanium dioxide powder apparatus for producing |
| CN105800677A (en) * | 2016-05-18 | 2016-07-27 | 云南林缘香料有限公司 | Production method and equipment for producing metatitanic acid through titanium dioxide slurry |
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-
2019
- 2019-05-27 CN CN201910447114.3A patent/CN110040775A/en active Pending
Patent Citations (10)
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|---|---|---|---|---|
| US5527469A (en) * | 1995-06-12 | 1996-06-18 | Lawhorne; Earl R. | Method for the preparation of desulfurized titanium oxide hydrolysate of high purity |
| WO1999043616A1 (en) * | 1998-02-24 | 1999-09-02 | Rotem Amfert Negev Ltd. | A modified titanium dioxide and a method for its preparation |
| CN1539745A (en) * | 2003-10-28 | 2004-10-27 | 南宁一泓环境工程有限公司 | Filterpressing, washing, cleansing processes for manufacturing hydration titania |
| CN101092245A (en) * | 2007-07-09 | 2007-12-26 | 朱贤荣 | Methods for preparing and using crystal seeds of rutile in high activity |
| CN103030175A (en) * | 2012-12-29 | 2013-04-10 | 上海安赐机械设备有限公司 | Device and method applied to metatitanic acid washing room |
| CN103531363A (en) * | 2013-10-24 | 2014-01-22 | 攀枝花学院 | Preparation method of slurry for photoanode of nano TiO2 membrane of dye-sensitized solar cell |
| CN204873875U (en) * | 2015-01-09 | 2015-12-16 | 上海安赐机械设备有限公司 | Green sulfate process titanium dioxide powder apparatus for producing |
| CN104828861A (en) * | 2015-05-13 | 2015-08-12 | 攀枝花学院 | Method for producing pigment titanium dioxide by performing industrial metatitanic acid size grading |
| CN105800677A (en) * | 2016-05-18 | 2016-07-27 | 云南林缘香料有限公司 | Production method and equipment for producing metatitanic acid through titanium dioxide slurry |
| CN106241863A (en) * | 2016-06-30 | 2016-12-21 | 广西金茂钛业有限公司 | A kind of catalyst pure titanium valve and the production method of low-sulfur titanium dioxide |
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