CN104261468A - Production method of low-alkali metal catalytic titanium dioxide - Google Patents
Production method of low-alkali metal catalytic titanium dioxide Download PDFInfo
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- CN104261468A CN104261468A CN201410480446.9A CN201410480446A CN104261468A CN 104261468 A CN104261468 A CN 104261468A CN 201410480446 A CN201410480446 A CN 201410480446A CN 104261468 A CN104261468 A CN 104261468A
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- C01—INORGANIC CHEMISTRY
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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Abstract
The invention discloses a production method of low-alkali metal catalytic titanium dioxide. The production method comprises the following steps: performing acidolysis, crystallization, concentration, hydrolysis, primary washing, bleaching, secondary washing, salt treatment, calcination and crushing sequentially, performing suction filtration and pulping on metatitanic acid which is qualified in secondary washing after salt treatment and before calcination to 320-380g/l, uniformly stirring, then taking 1000ml, placing into a clean beaker, continuously stirring, simultaneously adding 115ml of ammonia water solution with the mass fraction of 20%, uniformly stirring, heating the beaker in a constant-temperature water bath pot at the temperature of 85-95 DEG C, heating while stirring till the temperature of a mixed solution in the beaker achieves 80-90 DEG C, performing heat preservation for 1h, then taking out the beaker, cooling to 35-50 DEG C, adding an ethanol solution in the volume ratio to metatitanic acid of 1: (5-10) and the mass fraction of 75%, stirring for 25-60min, then performing suction filtration, taking a filter cake, drying, grinding and then tabletting. The production method disclosed by the invention has the beneficial effects that the product contains few alkali metals and has a small particle size, and crushing and grading are not required.
Description
Technical field
The present invention relates to denitration catalyst titanium white production technical field, particularly relate to a kind of making method of low alkali catalysis titanium white.
Background technology
TiO
2as a kind of new function material, with the catalyzer that it makes carrier have active high, selectivity good, anti-toxic is strong, low temperature active good, surface acidity is adjustable and the advantage such as high temperature vattability, although the research of each side is ripe all not enough at present, but the huge applications potentiality shown by it can not be ignored, many scholars think, TiO
2the SiO that continues will be become
2, Al
2o
3third generation support of the catalyst afterwards.The main raw material of the titanium dioxide that market is sold is exactly TiO
2the production technique of sulfuric acid method titanium pigment generally comprises acidolysis, crystallization, concentrated, hydrolysis, is washed, bleach, two wash, Ficus caricaL, calcining and pulverizing, its technical process described in detail in " sulfuric acid method titanium pigment production " literary composition, at present, an alkali metal salt contained in obtained in this way catalysis titanium white finished product and K, Na ion are generally at about 100ppm.In well-known catalysis titanium white, the slightly high poisoning of catalyst that will make of the alkali metal content such as potassium, sodium lost efficacy.And the most of factory of existing technique all adopts alkalimetal ions most in the de-mineralized water of the removing washings such as negative and positive leaving office exchange resin or semi-transparent embrane method, the result of this technique is that the alkali metal salt content in the finished product is almost consistent with the content of de-mineralized water, cannot accomplish the object reduced further again.
Summary of the invention
The technical problem to be solved in the present invention is that existing titanium white production technique effectively can not remove basic metal, provides a kind of making method of low alkali catalysis titanium white for this reason.
Technical scheme of the present invention is: a kind of making method of low alkali catalysis titanium white, it comprises the following steps: acidolysis, crystallization, concentrated, hydrolysis, one washes, bleaching, two wash, Ficus caricaL, calcining and pulverizing, it is characterized in that after Ficus caricaL completes, before calcining, washing qualified metatitanic acid suction filtration making beating by two to 320-380g/l, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, the thermostat water bath of beaker as 85-95 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 80-90 °, take out beaker after insulation 1h and be cooled to 35-50 DEG C, add and metatitanic acid volume ratio 1:(5-10) massfraction be the ethanolic soln of 75%, suction filtration after stirring 25-60min, get filter cake oven dry and grind rear compressing tablet.
Described in such scheme, two wash qualified metatitanic acid suction filtration making beating to 360 g/l.
Take out after the insulation of beaker described in such scheme 1h and be cooled to 40 DEG C.
The ethanolic soln added described in such scheme and metatitanic acid volume ratio 1:10, massfraction is 75%.
Through embrittlement process before pulverizing after calcining described in such scheme, described embrittlement process comprises irradiates 10-30min by the material hard X ray obtained after calcining, more suddenly freezes 3-7min under-5-0 °.
The invention has the beneficial effects as follows and add 75% ethanolic soln in proportion in order to absorb an alkali metal salt in inclined material once again in Ficus caricaL operation.Ethanolic soln own alkali-free metal ion and can arbitrary proportion water-soluble, therefore the effect of again dissolving an alkali metal salt can be accomplished.And ethanolic soln is removed by press filtration in squeezing process afterwards, remain in material ethanol then rotary kiln calcining process in volatilization or burning and remove, to ensure the pure of product, the product caustic soda metal salt concentration obtained with this technology can be down to below 40ppm.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1: wash qualified metatitanic acid suction filtration making beating before calcining by two to 320g/l after Ficus caricaL completes, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, surveying PH is afterwards 10.7, the thermostat water bath of beaker as 85 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 80 °, recording PH after insulation 1h is 10.4, take out beaker and be cooled to 35 DEG C, the massfraction adding 50ml is the ethanolic soln of 75%, suction filtration after stirring 25min, get filter cake oven dry and grind rear compressing tablet.
Embodiment 2: wash qualified metatitanic acid suction filtration making beating before calcining by two to 360g/l after Ficus caricaL completes, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, surveying PH is afterwards 11, the thermostat water bath of beaker as 95 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 90 °, recording PH after insulation 1h is 10.5, take out beaker and be cooled to 50 DEG C, the massfraction adding 67ml is the ethanolic soln of 75%, suction filtration after stirring 40min, get filter cake oven dry and grind rear compressing tablet.
Embodiment 3: wash qualified metatitanic acid suction filtration making beating before calcining by two to 380g/l after Ficus caricaL completes, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, surveying PH is afterwards 10.8, the thermostat water bath of beaker as 90 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 85 °, recording PH after insulation 1h is 11.7, take out beaker and be cooled to 40 DEG C, the massfraction adding 100ml is the ethanolic soln of 75%, suction filtration after stirring 30min, get filter cake oven dry and grind rear compressing tablet.
Embodiment 4: wash qualified metatitanic acid suction filtration making beating before calcining by two to 360g/l after Ficus caricaL completes, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, surveying PH is afterwards 10.7, the thermostat water bath of beaker as 90 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 85 °, recording PH after insulation 1h is 10.3, take out beaker and be cooled to 40 DEG C, the massfraction adding 200ml is the ethanolic soln of 75%, suction filtration after stirring 30min, get filter cake oven dry and grind rear compressing tablet.
Embodiment 5: wash qualified metatitanic acid suction filtration making beating before calcining by two to 360g/l after Ficus caricaL completes, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, surveying PH is afterwards 11.2, the thermostat water bath of beaker as 90 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 85 °, recording PH after insulation 1h is 10.5, take out beaker and be cooled to 50 DEG C, the massfraction adding 100ml is the ethanolic soln of 75%, suction filtration after stirring 30min, get filter cake oven dry and grind rear compressing tablet.
Embodiment 6: wash qualified metatitanic acid suction filtration making beating before calcining by two to 360g/l after Ficus caricaL completes, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, surveying PH is afterwards 10.9, the thermostat water bath of beaker as 90 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 85 °, recording PH after insulation 1h is 10.6, take out beaker and be cooled to 45 DEG C, the massfraction adding 100ml is the ethanolic soln of 75%, suction filtration after stirring 30min, get filter cake oven dry and grind rear compressing tablet.
Embodiment 7: wash qualified metatitanic acid suction filtration making beating before calcining by two to 360g/l after Ficus caricaL completes, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, surveying PH is afterwards 11.1, the thermostat water bath of beaker as 90 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 85 °, recording PH after insulation 1h is 10.7, take out beaker and be cooled to 40 DEG C, the massfraction adding 100ml is the ethanolic soln of 75%, suction filtration after stirring 30min, get filter cake oven dry and grind rear compressing tablet.
Embodiment 8: wash qualified metatitanic acid suction filtration making beating before calcining by two to 360g/l after Ficus caricaL completes, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, surveying PH is afterwards 11.1, the thermostat water bath of beaker as 90 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 85 °, recording PH after insulation 1h is 10.2, take out beaker and be cooled to 35 DEG C, the massfraction adding 100ml is the ethanolic soln of 75%, suction filtration after stirring 30min, get filter cake oven dry and grind rear compressing tablet.
Be that the compressing tablet of the Ethanol Treatment of 75% is designated as embodiment 9 without massfraction, qualified metatitanic acid suction filtration making beating is washed before calcining by two to 360g/l after Ficus caricaL completes, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, surveying PH is afterwards 10.5, the thermostat water bath of beaker as 90 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 85 °, recording PH after insulation 1h is 10.2, suction filtration after stirring 30min, gets filter cake oven dry and grinds rear compressing tablet.
Na ionic concn, K ionic concn diffractometer contained by the compressing tablet of embodiment 1-10 gained are detected, correlation data is as shown in the table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Na+ | 85ppm | 77ppm | 39ppm | 30ppm | 98ppm | 68ppm | 39ppm | 33ppm | 130ppm |
| K+ | 85ppm | 70ppm | 32ppm | 27ppm | 92ppm | 58ppm | 32ppm | 29ppm | 125ppm |
As can be seen from the above table, add massfraction 75% ethanolic soln and effectively can absorb K, Na ion in material, in finished product, alkali metal salt content can effectively reduce; Material with add volumes of aqueous ethanol than controlling at 10:1.Ethanol added K, Na ionic absorption DeGrain at least, and the while that time too much, assimilation effect promoting not obvious, production cost is high; During the interpolation of ethanolic soln, temperature of charge optimum is at 40 degree.The volatilization of temperature too high ethanol is serious, and assimilation effect is poor; Then length consuming time, energy consumption are large in process of production for too low material.
In press filtration operation, ethanolic soln is filtered and squeezes and be separated, and part is residual then volatilizees or burns and remove in the process of rotary kiln calcining.Filtrate portion need collect, and uses that separation column is separated again, purifying ethanol and ammoniacal liquor, to reach the recycling of ethanolic soln, reduces production cost.
The present invention is that the material obtained on the basis of above-described embodiment 1-9 eliminates residual ethanol after firing, obtain pure titanium dioxide granule, if directly titanium dioxide granule is carried out fragmentation, due to some bonding of the material after calcining, special equipment such as Raymond machine is needed to carry out fragmentation, again through the classification of classifying turbine, material feeding feed screw after pulverizing is delivered to finished product bin, complex steps, use Raymond machine and classifying turbine energy consumption higher, preference of the present invention is the step of adding a brittle process between calcining and pulverizing for this reason, some bonding dry materials can be separated refinement, save step that is broken and classification, shorten technical process, increase work efficiency.
Particularly, preferred embodiment 10: the material hard X ray obtained after calcining is irradiated 10min, suddenly 3min is frozen again under-5 °, after hard X ray is irradiated, material can be dry, can not be bonding between material particles, then freeze process through too urgent, material can be brittle fast, be refined into evengranular particulate, without the need to passing through broken and classification, can directly as finished product.
Preferred embodiment 11: the material hard X ray obtained after calcining is irradiated 30min, more suddenly freeze 7min at 0.
Hard X ray irradiation time can not be too short, otherwise do not have the effect of dried material, also can not be long, and long meeting causes the unstable chemcial property of material, the temperature of suddenly freezing can not too low also can not be too high, otherwise material particular diameter can not produce brittle reaction.Data Comparison sees the following form:
| Condition | Size |
| Hard X ray irradiates 8min, and-7 ° of urgency freeze 1min | 200nmn |
| Hard X ray irradiates 10min, and-5 ° of urgency freeze 3min | 100nmn |
| Hard X ray irradiates 20min, and-2 ° of urgency freeze 5min | 96nmn |
| Hard X ray irradiates 30min, and 0 ° of urgency freezes 7min | 97nmn |
| Hard X ray irradiates 35min, and 0 ° of urgency freezes 8min | 204nmn |
Claims (5)
1. the making method of a low alkali catalysis titanium white, it comprises the following steps: acidolysis, crystallization, concentrated, hydrolysis, one washes, bleaching, two wash, Ficus caricaL, calcining and pulverizing, it is characterized in that after Ficus caricaL completes, before calcining, washing qualified metatitanic acid suction filtration making beating by two to 320-380g/l, get 1000ml after stirring evenly and put into clean beaker continuation stirring, add massfraction be the ammonia soln 115ml of 20% and stir simultaneously, the thermostat water bath of beaker as 85-95 ° is heated up, the mixing solutions temperature that intensification limit, limit is stirred in beaker reaches 80-90 °, take out beaker after insulation 1h and be cooled to 35-50 DEG C, add and metatitanic acid volume ratio 1:(5-10) massfraction be the ethanolic soln of 75%, suction filtration after stirring 25-60min, get filter cake oven dry and grind rear compressing tablet.
2. the making method of a kind of low alkali catalysis titanium white as claimed in claim 1, is characterized in that described two wash qualified metatitanic acid suction filtration making beating to 360 g/l.
3. the making method of a kind of low alkali catalysis titanium white as claimed in claim 2, takes out after it is characterized in that described beaker insulation 1h and is cooled to 40 DEG C.
4. the making method of a kind of low alkali catalysis titanium white as claimed in claim 3, the ethanolic soln added described in it is characterized in that and metatitanic acid volume ratio 1:10, massfraction is 75%.
5. the making method of a kind of low alkali catalysis titanium white as described in as arbitrary in claim 1-4, through brittle process before pulverizing after it is characterized in that described calcining, described embrittlement process comprises irradiates 10-30min by the material hard X ray obtained after calcining, more suddenly freezes 3-7min under-5-0 °.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106379936A (en) * | 2016-08-31 | 2017-02-08 | 南京钛白化工有限责任公司 | Preparation method of high specific surface area titanium dioxide for denitration catalyst |
| CN107298460A (en) * | 2017-05-22 | 2017-10-27 | 超彩环保新材料科技有限公司 | Titanium dioxide of low-sulfur superhigh specific surface area and preparation method thereof and purposes |
| CN112473640A (en) * | 2020-12-09 | 2021-03-12 | 安徽迪诺环保新材料科技有限公司 | Method for micro-adjusting pore volume and pore diameter of nano titanium dioxide for flue gas denitration catalyst |
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| EP2578537A2 (en) * | 2010-05-26 | 2013-04-10 | Industry-University Cooperation Foundation Sogang University | Novel method for producing titanium dioxide particles, and titanium dioxide particles produced thereby |
| CN103112892A (en) * | 2013-02-27 | 2013-05-22 | 王泽洪 | Production method of nano titanium white |
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Patent Citations (3)
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|---|---|---|---|---|
| EP2578537A2 (en) * | 2010-05-26 | 2013-04-10 | Industry-University Cooperation Foundation Sogang University | Novel method for producing titanium dioxide particles, and titanium dioxide particles produced thereby |
| CN102391689A (en) * | 2011-08-11 | 2012-03-28 | 四川龙蟒钛业股份有限公司 | Preparation method of high dispersing rutile product |
| CN103112892A (en) * | 2013-02-27 | 2013-05-22 | 王泽洪 | Production method of nano titanium white |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106379936A (en) * | 2016-08-31 | 2017-02-08 | 南京钛白化工有限责任公司 | Preparation method of high specific surface area titanium dioxide for denitration catalyst |
| CN107298460A (en) * | 2017-05-22 | 2017-10-27 | 超彩环保新材料科技有限公司 | Titanium dioxide of low-sulfur superhigh specific surface area and preparation method thereof and purposes |
| CN107298460B (en) * | 2017-05-22 | 2020-01-07 | 超彩环保新材料科技有限公司 | Low-sulfur titanium dioxide with ultrahigh specific surface area, and preparation method and application thereof |
| CN112473640A (en) * | 2020-12-09 | 2021-03-12 | 安徽迪诺环保新材料科技有限公司 | Method for micro-adjusting pore volume and pore diameter of nano titanium dioxide for flue gas denitration catalyst |
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