CN107629482B - Preparation method of nano bismuth vanadate orange inorganic pigment - Google Patents
Preparation method of nano bismuth vanadate orange inorganic pigment Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 43
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 42
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000001023 inorganic pigment Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000012716 precipitator Substances 0.000 claims abstract description 12
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 12
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002752 molybdenum compounds Chemical class 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- LOUBVQKDBZRZNQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.[V+5] Chemical compound [O-2].[O-2].[OH-].O.[V+5] LOUBVQKDBZRZNQ-UHFFFAOYSA-M 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000006911 nucleation Effects 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 5
- 238000004321 preservation Methods 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 239000000049 pigment Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000001053 orange pigment Substances 0.000 description 3
- 239000001054 red pigment Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- -1 and after filtration Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention provides a preparation method of a nano bismuth vanadate orange inorganic pigment, which comprises the following steps: respectively dissolving a bismuth compound and a vanadium compound in dilute nitric acid, dissolving a molybdenum compound in water, dissolving aluminum nitrate, cerium nitrate and zinc nitrate in dilute nitric acid, and filtering for later use; then mixing and stirring the solution uniformly and then heating; dropwise adding a precipitator into the reaction solution until the pH value is 4-7, and stirring while keeping the temperature until the precipitation is complete; heating the solution to reflux temperature, adjusting pH to 7-12, and stirring and aging at the reflux temperature until the precipitate is coarse and the color is converted into light yellow; drying the precipitate after filtering to obtain a loose nano orange bismuth vanadate precursor; and finally, placing the precursor in a muffle furnace, heating to the crystal conversion temperature, and cooling to room temperature after heat preservation. The invention can adjust the hue, control the nucleation and growth speed, prepare the nano-scale bismuth vanadate orange powder with very small and uniform particle size and has low manufacturing cost.
Description
Technical Field
The invention belongs to the technical field of pigment preparation, and particularly relates to a preparation method of a nano bismuth vanadate orange inorganic pigment.
Background
The environmental protection problem is more and more widely concerned by the international society, and the development of low-carbon and environment-friendly products, energy conservation and emission reduction are important means for dealing with the increasingly worsened environment and resource shortage. At present, orange pigments in the market are mainly organic orange and have the defects of insufficient temperature resistance and weather resistance, inorganic orange pigments are blended by cadmium red, cerium sulfide red, bismuth vanadate yellow and the like, a single orange inorganic pigment market does not exist, the cadmium red pigments contain toxic heavy metals and have great hidden danger to the environment and personal safety, the developed countries abroad definitely forbid production, and domestic enterprises stop production and settle down in succession, so that the development of the inorganic environment-friendly pigments with orange tone is significant.
In the prior art, the preparation of the nano inorganic pigment mainly comprises a solid-phase ball milling method, a liquid-phase method, a sol-gel method and a complexation method, wherein the solid-phase ball milling process has higher requirements on equipment, requires high-speed ball milling for a long time, causes more impurities and serious unevenness, and cannot produce high-end products; the liquid phase precipitation method is a general method for preparing high-end powder at present, the liquid phase precipitation method is a molecular level contact method, the contact can be fully achieved, the process flow comprises liquid phase synthesis, rinsing, drying, calcining, ball milling post-treatment and the like, the production process is relatively long, a large amount of wastewater is brought, and the treatment cost is high; the sol-gel method and the complexation method have high raw material cost, and are not beneficial to industrialization.
Therefore, it is necessary to solve the above-mentioned drawbacks.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a nano bismuth vanadate orange inorganic pigment, which can be used for preparing nano bismuth vanadate orange powder with very small and uniform particle size by controlling nucleation and growth speed and has low cost.
The invention provides a preparation method of a nano bismuth vanadate orange inorganic pigment, which comprises the following steps:
respectively dissolving a bismuth compound and a vanadium compound in 1mol/L dilute nitric acid, and filtering for later use; meanwhile, dissolving the molybdenum compound in 100ml of water, and filtering for later use;
respectively dissolving aluminum nitrate, cerium nitrate and zinc nitrate in 1mol/L dilute nitric acid, and filtering for later use; wherein Al in the aluminum nitrate3+With Bi in the bismuth compound3+The mixture ratio is Al3+∶Bi3+0.05-0.2: 1; ce in the cerium nitrate4+And in the bismuth compoundOf Bi3+The mixture ratio is Ce4+∶Bi3+0.02-0.1: 1; zn in the zinc nitrate2+With Bi in the bismuth compound3+The mixture ratio is Zn2+∶Bi3+＝0.05-0.1∶1；
Mixing and stirring the solutions uniformly, heating to 30-60 ℃, then slowly dripping 25-30% ammonia water serving as a precipitator into the reaction solution at the speed of 30-40ml/min, stopping dripping the precipitator when the pH value is titrated to 4-7, and keeping stirring for 1-3 hours at the temperature until the precipitation is complete;
after the precipitation is complete, the solution is warmed to reflux temperature80℃-99℃Adjusting the pH value to 7-12, stopping dropwise adding the precipitator, and continuously stirring and curing at the reflux temperature until the precipitate is coarse and the color is converted into light yellow;
filtering the precipitate, and drying in a drying oven to obtain a loose nano-scale orange bismuth vanadate precursor;
placing the precursor in a muffle furnace, heating to a crystal conversion temperature, preserving heat for a period of time, and naturally cooling to room temperature;
in the above steps of the invention, the ratio of bismuth compound to vanadium compound is 1: 1-1.2.
In the above step of the present invention, Mo in the molybdenum compound6+And V in the vanadium compound5+The proportion is Mo6+∶V5+＝0.05-0.2∶1。
In the above steps of the invention, the bismuth compound is at least one of bismuth nitrate, bismuth trioxide and metal bismuth powder.
In the above steps of the invention, the vanadium compound is at least one of ammonium metavanadate, vanadium pentoxide and vanadium tetraoxide.
In the above steps of the present invention, the molybdenum compound is at least one of ammonium molybdate and sodium molybdate.
The invention adopts a liquid phase precipitation method process, can prepare uniform nano-scale particles with very fine particle size by controlling nucleation and growth speed, and can rapidly crystallize in a short time only by increasing temperature and pH value in a later curing stage due to very high surface free energy to form nano-powder with very high crystallinity. In addition, in the whole synthesis process, impurity ions such as alkali metal and the like do not need to be introduced, after calcination, the agglomeration of the powder is very small, and the target powder can be obtained only by simple post-treatment. The powder obtained by the method has bright color, narrow particle size distribution interval and strong tinting strength; the product hue is between the bismuth vanadate yellow pigment and the market red pigment, the hue can be adjusted according to the proportion, the product is bright orange powder, can be directly used, does not need color matching, is convenient to use, and fills the market blank.
As can be seen from the steps, the production process of the invention has the advantages of simple flow, short process time, low cost, low energy consumption and easy realization of large-scale production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a nano bismuth vanadate orange inorganic pigment, which comprises the following steps:
s1, respectively dissolving the bismuth compound and the vanadium compound in 1mol/L dilute nitric acid, and filtering for later use; and dissolving the molybdenum compound in water, and filtering for later use.
In the step, the bismuth compound can be at least one of bismuth nitrate, bismuth trioxide and metal bismuth powder; the vanadium compound is at least one of ammonium metavanadate, vanadium pentoxide and vanadium tetraoxide; the molybdenum compound is selected from at least one of ammonium molybdate and sodium molybdate. Wherein the weight ratio of the bismuth compound to the vanadium compound is 1: 1-1.2, the bismuth compound and the vanadium compound are respectively dissolved in 1mol/L dilute nitric acid solution, the solution is filtered, and a certain amount of deionized water is added to adjust the concentration of the solution to be 0.5 mol/L. The amount of the molybdenum compound depends on the vanadium compound in which V is present5+And Mo in the middle6+The mixture ratio is V5+∶Mo6+＝1∶0.05-0.2。
In the step, bismuth compounds and vanadium compounds are dissolved in dilute nitric acid to form bismuth vanadate, a certain content of molybdenum compounds are added to form bismuth molybdate, the effect of adjusting color is achieved, orange with different chroma can be adjusted according to the ratio of vanadium/molybdenum, and the higher the ratio of vanadium/molybdenum is, the stronger the orange color tone is.
S2, respectively dissolving aluminum nitrate, cerium nitrate and zinc nitrate in 1mol/L dilute nitric acid, and filtering for later use.
This step introduces Al3+、Ce4+、Zn2+Ions can dope bismuth vanadate, wherein aluminum nitrate { Al (NO) is added3)3Zinc nitrate { Zn (NO) }3)2The pigment can play a role in mineralization, reduce the calcination temperature and improve the brightness of the pigment; adding cerium nitrate { Ce (NO)3)4The hue of the product can be adjusted to be between that of yellow and red bismuth vanadate, and Ce (NO)3)4The higher the content, the higher the red hue.
In this step, the aluminum nitrate { Al (NO) }3)3Al in (1) }3+With Bi of the bismuth compound3+The mixture ratio is Al3+∶Bi3+0.05-0.2: 1; cerium nitrate { Ce (NO)3)4Ce in (1)4+With Bi of the bismuth compound3+The mixture ratio is Ce4+∶Bi3+0.02-0.1: 1; zinc nitrate { Zn (NO)3)2Zn in (b) }2+With Bi of the bismuth compound3+The mixture ratio is Zn2+∶Bi3+0.05-0.1: 1. The proportion can ensure that the color of the final product has beautiful orange.
S3, filtering the solution, respectively adding the prepared vanadium solution, molybdenum solution, aluminum nitrate solution, cerium nitrate solution and zinc nitrate solution into the bismuth solution, mixing and stirring uniformly, slowly heating to 30-60 ℃, preferably 50 ℃ to ensure that the materials are fully and uniformly mixed before the reaction, so that the reaction is more complete.
Then, slowly dripping a precipitator into the reaction liquid at a certain speed, slowly forming bismuth vanadate, bismuth molybdate, aluminum hydroxide and cerium hydroxide precipitates along with the continuous addition of the precipitator, stopping dripping the precipitator when the pH value of the solution reaches 4-7 by titration, and keeping stirring for 1-3 hours under the temperature until the precipitation is complete.
In the step, ammonia water with the concentration of 25% -30% is selected as a precipitator, the speed is 30-40ml/min, the pH value is preferably 6, and the heat preservation time is preferably 2 hours. By maintaining the pH value and a certain reaction time, the nucleation and growth speed can be controlled, which is beneficial to the homogenization of the precipitated particles.
After precipitation of S4 is complete, the solution is warmed to reflux temperature 80-99 deg.C, preferably 90 deg.C, and then adjusted to raise the pH to 7-12, preferably 8.
In the step, the pH value is increased to form zinc hydroxide precipitate, and meanwhile, the temperature is increased to facilitate the crystal form conversion and form particles with a certain crystal structure. At this reflux temperature, the aging was continued with stirring until the precipitate became coarse and the color turned to pale yellow.
S5, filtering the precipitate, and drying in a drying oven at 85 ℃ for 3-5 hours to remove moisture or other impurities in the precipitate to obtain a loose nano orange bismuth vanadate precursor.
S6, placing the precursor in a muffle furnace, heating to the crystal conversion temperature of-650 ℃ at the speed of 60 ℃/min, preserving the temperature for 2 hours, and naturally cooling to the room temperature.
In the step, high-temperature crystal conversion can be carried out through calcination at a certain temperature and heat preservation for a certain time, so that pigment powder with a special structure and a crystal form is formed.
In the steps of the invention, a liquid-phase precipitation process is adopted, aluminum nitrate, cerium nitrate and zinc nitrate are introduced to play an ion doping role in bismuth vanadate, the hue of the final finished product can be adjusted, the obtained product hue is between that of bismuth vanadate yellow pigment and market red pigment, bright orange powder is formed, and the color effect is effectively improved. Meanwhile, a precipitator is added dropwise and the pH of the solution is adjusted, so that nucleation and growth speed can be controlled, and uniform nano-scale particles with very small particle size can be prepared. Because the particles are small and the surface free energy is very high, the nano powder with very high crystallinity can be quickly crystallized in a short time only by increasing the temperature and the pH value in the later curing stage. In addition, in the whole synthesis process, impurity ions such as alkali metal and the like do not need to be introduced, after calcination, the agglomeration of the powder is very small, and the target powder can be obtained only by simple post-treatment.
The preparation method disclosed by the invention is simple in preparation process and low in cost, the obtained powder is narrow in particle size distribution interval, bright in color and strong in tinting strength due to bright orange color, can be directly used, does not need color matching, is convenient to use, and fills the gap of inorganic orange pigments in the market.
The present invention will be described in further detail with reference to examples.
Example 1:
1. weighing Bi (NO)3)348.5 g, NH4VO312.87 g, dissolved in 50ml of 1mol/L nitric acid, filtered, and added with water to reach the constant concentration of 0.5 mol/L. Ammonium molybdate 1.94 g was weighed, dissolved in 100ml of water and filtered for use.
2. Weighing Zn (NO)3)32.86 g, 0.85 g of cerous nitrate and 2.5 g of aluminum nitrate are dissolved in 1mol/L of dilute nitric acid and filtered for standby. And respectively adding the prepared solutions into a bismuth nitrate solution, continuously stirring for ten minutes, uniformly mixing, and heating to 50 ℃.
3. Dropping 28% ammonia water into the reaction solution at the speed of 30ml/min, with the increase of pH, a large amount of light yellow precipitate appears, detecting the change by a pH meter, when the pH reaches 6, stopping titrating the precipitant, and keeping stirring at the temperature for 2 hours until the precipitate is complete.
4. The temperature was raised to 90 ℃ and the titration of ammonia was continued until pH 8, at which point the titration was stopped and stirring was continued for 1 hour until a pale yellow precipitate appeared.
5. And (3) carrying out vacuum filtration on the reaction liquid at room temperature, and drying the filter cake in an oven at 85 ℃ for 4 hours to obtain an orange bismuth vanadate pigment precursor.
6. The precursor is placed in a muffle furnace, the temperature is raised to 650 ℃ at the speed of 60 ℃/min, the temperature is kept for 2 hours, and the precursor is naturally cooled to the room temperature.
45.6 g of orange bismuth vanadate pigment are obtained with the following composition analysis: bi2O3：61％、V2O5：28.5％、MoO3：3.25％、ZnO：1.2％、Al2O3：1.86％、CeO2：0.8％。
Example 2:
1. weighing Bi2O323.3 g, V2O59.1 g of the aqueous solution is dissolved in 50ml of 1mol/L nitric acid, and after filtration, water is added to the solution until the concentration is 0.5 mol/L. 2.4 g of sodium molybdate is weighed, dissolved in 100ml of water and filtered for use.
2. Weighing Zn (NO)3)21.45 g, 0.85 g of cerous nitrate and 1.2 g of aluminum nitrate are dissolved in 1mol/L of dilute nitric acid and filtered for standby. And respectively adding the prepared solutions into a bismuth nitrate solution, continuously stirring for ten minutes, uniformly mixing, and heating to 50 ℃.
3. Dropping 30% ammonia water into the reaction solution at the speed of 30ml/min, with the increase of pH, a large amount of light yellow precipitate appears, detecting the change by a pH meter, when the pH reaches 6, stopping titrating the precipitant, and keeping stirring at the temperature for 2 hours until the precipitate is complete.
4. The temperature was raised to 90 ℃ and the titration of ammonia was continued until pH 8, at which point the titration was stopped and stirring was continued for 1.5 hours until a pale yellow precipitate appeared.
5. And (3) carrying out vacuum filtration on the reaction liquid at room temperature, and drying the filter cake in an oven at 90 ℃ for 4 hours to obtain an orange bismuth vanadate pigment precursor.
6. The precursor is placed in a muffle furnace, the temperature is raised to 650 ℃ at the speed of 60 ℃/min, the temperature is kept for 2 hours, and the precursor is naturally cooled to the room temperature.
44.5 g of orange bismuth vanadate pigment are obtained with the following analysis: bi2O3：62％、V2O5：28.6％、MoO3：3.15％、Al2O3：0.6％、ZnO：1.24％、CeO2：0.82％。
In summary, the above-mentioned embodiments of the present invention are only part of the preferred embodiments of the present invention, and the present invention is not limited thereto, and those skilled in the art can make modifications, equivalent substitutions and improvements without departing from the spirit of the present invention, and thus the scope of the present invention is covered.
Claims (5)
1. A preparation method of nano bismuth vanadate orange inorganic pigment is characterized by comprising the following steps:
respectively dissolving bismuth compound and vanadium compound in the weight ratio of 1: 1-1.2 in 1mol/L dilute nitric acid, filtering, and adding deionized water to adjust the concentration of the solution to 0.5mol/L for later use; meanwhile, dissolving the molybdenum compound in 100ml of water, and filtering for later use;
respectively dissolving aluminum nitrate, cerium nitrate and zinc nitrate in 1mol/L dilute nitric acid, and filtering for later use; wherein Al in the aluminum nitrate3+With Bi in the bismuth compound3+The mixture ratio is Al3+∶Bi3+0.05-0.2: 1; ce in the cerium nitrate4+With Bi in the bismuth compound3+The mixture ratio is Ce4+∶Bi3+0.02-0.1: 1; zn in the zinc nitrate2+With Bi in the bismuth compound3+The mixture ratio is Zn2+∶Bi3+＝0.05-0.1∶1；
Mixing and stirring the solutions uniformly, heating to 30-60 ℃, then slowly dripping 25-30% ammonia water serving as a precipitator into the reaction solution at the speed of 30-40ml/min, stopping dripping the precipitator when the pH value is titrated to 4-7, and keeping stirring for 1-3 hours at the temperature until the precipitation is complete;
after the precipitation is completed, heating the solution to the reflux temperature of 80-99 ℃, adjusting the pH value to 7-12, stopping dropwise adding the precipitator, and continuously stirring and curing at the reflux temperature until the precipitate is coarse and the color is converted into light yellow;
filtering the precipitate, and drying in a drying oven to obtain a loose nano-scale orange bismuth vanadate precursor;
and (3) placing the precursor in a muffle furnace, heating to the crystal conversion temperature, preserving the temperature for a period of time, and naturally cooling to room temperature.
2. The method of claim 1, wherein the molybdenum is combined with the orange nano-bismuth vanadate pigmentIn the material Mo6+And V in the vanadium compound5+The proportion is Mo6+∶V5+＝0.05-0.2∶1。
3. The method for preparing nano bismuth vanadate orange inorganic pigment according to claim 1 or 2, wherein the bismuth compound is at least one of bismuth nitrate, bismuth trioxide and metal bismuth powder.
4. The method for preparing nano bismuth vanadate orange inorganic pigment according to claim 1 or 2, wherein the vanadium compound is at least one of ammonium metavanadate, vanadium pentoxide and vanadium tetraoxide.
5. The method for preparing nano bismuth vanadate orange inorganic pigment according to claim 1 or 2, wherein the molybdenum compound is selected from at least one of ammonium molybdate and sodium molybdate.
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| CN109181363A (en) * | 2018-10-12 | 2019-01-11 | 湖南汉瑞新材料科技有限公司 | A kind of bismuth vanadate yellow pigment and preparation method thereof |
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| CN110790311B (en) * | 2019-11-26 | 2022-04-05 | 湖南三丰钒业有限公司 | Preparation method of vanadium bismuth persimmon red and application of vanadium bismuth persimmon red as pigment |
| CN115367798B (en) * | 2022-08-22 | 2023-08-25 | 深圳力合通科技有限公司 | Method for preparing environment-friendly pigment by utilizing industrial waste vanadium material |
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