CN115806745B - Composite nano transparent iron oxide red and preparation method thereof - Google Patents
Composite nano transparent iron oxide red and preparation method thereof Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 43
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 32
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 23
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 20
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 20
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000004576 sand Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000004277 Ferrous carbonate Substances 0.000 claims abstract description 8
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000019268 ferrous carbonate Nutrition 0.000 claims abstract description 8
- 229960004652 ferrous carbonate Drugs 0.000 claims abstract description 8
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims abstract description 7
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000010215 titanium dioxide Nutrition 0.000 claims abstract description 5
- 239000011247 coating layer Substances 0.000 claims abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000231392 Gymnosiphon Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a composite nano transparent iron oxide red and a manufacturing method thereof. The preparation method of the composite nano transparent iron oxide red comprises the following steps: mixing a ferrous sulfate solution and a high-purity barium carbonate solution, grinding by a nano sand mill, and reacting the barium carbonate with the ferrous sulfate to form ferrous carbonate, ferrous hydroxide and barium sulfate under the condition of high-energy collision refinement of the nano sand mill; after the grinding reaction is finished, the grinding is carried out at a slow speed, and then air is introduced to oxidize ferrous hydroxide into ferric oxide, so that the nano ferric oxide forms a compact coating layer on the surface of nano barium sulfate; and then carrying out hydrothermal treatment by using a hydrothermal reaction kettle, and drying at a low temperature to obtain the composite nano transparent iron oxide red. The method of the invention basically has no byproduct and pollutant, reduces the synthesis cost and solves the problem of the destination of the titanium white byproduct ferrous sulfate.
Description
Technical Field
The invention relates to a preparation method of inorganic pigment, in particular to composite nano transparent iron oxide red and a preparation method thereof.
Background
The basic chemical expression of the ferric oxide is Fe 2 O 3 There are a plurality of different forms such as a-type ferric oxide, and the ferric oxide with different forms presents different colors. The ferric oxide is nontoxic and cheap, and is an important base material with excellent performance in various fields such as building materials, coatings, rubber and the like. When the granularity of the ferric oxide reaches the nanometer level, the specific surface area, the surface energy and the like are obviously increased along with the reduction of the particle size, so that the effect of small size is highlighted, and especially the multiple scattering capability and the surface covering capability on visible light waves are reducedLow, but in a 'transparent' state, and simultaneously has a plurality of potential physical and chemical properties to be fully utilized, so that the transparent ferric oxide is widely applied in more fields.
The existing transparent iron oxide red has the problems of complex synthetic method, wide synthetic particle size distribution, difficult dispersion and the like. For example, chinese patent application publication No. CN102603010a, nanometer transparent iron oxide red, discloses a preparation method thereof: 1) Purifying and refining ferrous sulfate; 2) Preparing and oxidizing transparent iron oxide yellow seed crystal; 3) And preparing a transparent iron oxide red product. The invention takes ferrous sulfate as raw material and sodium carbonate as precipitant, firstly prepares ferrous carbonate for precipitation, then introduces air and adds composite additive, oxidizes ferrous carbonate into transparent iron oxide yellow, and prepares transparent iron oxide red by calcining iron oxide yellow at the calcining temperature of 300-500 ℃. The transparent pigment particles prepared by the method are in the shape of rice grains or approximately spindle, and the granularity of the product is controlled between 10 and 50 nanometers. However, the method is prepared by reacting sodium carbonate with ferrous sulfate and roasting, the process has the defects of high cost, complex roasting equipment, complex process, unstable product quality and serious pollution of sodium sulfate waste liquid generated in the filtering and rinsing process.
Disclosure of Invention
In view of the above, the invention provides a method for preparing composite nano transparent iron oxide red, which aims at the problems of high cost, complex process and the like caused by the large amount of raw materials for preparing transparent iron oxide red in the prior art, wherein the composite nano transparent iron oxide red is prepared by separating and purifying titanium white byproduct ferrous sulfate, mixing the titanium white byproduct ferrous sulfate with high-purity barium carbonate, grinding the mixture by a sand mill, adopting solid-liquid phase reaction, and generating reaction under the condition of high-energy collision refinement of the grinding mill. The invention is based on the improvement of raw materials and a reaction method, and in addition, the particle size of the product obtained by combining a hydrothermal mode is more concentrated than that of the product obtained by the traditional method, and the problem that the particle size is increased and difficult to disperse after sintering is avoided.
In order to solve the technical problems, the invention is realized by adopting the following technical scheme:
a method for manufacturing composite nano transparent iron oxide red comprises the following steps:
mixing ferrous sulfate solution and high-purity barium carbonate solution, grinding by a nano sand mill, and reacting the barium carbonate and the ferrous sulfate to form ferrous compounds (ferrous carbonate and ferrous hydroxide) and barium sulfate under the condition of high-energy collision refinement of the nano sand mill; the rotating speed of the nano sand mill at the stage is 2900r/min, and the grinding time is 180-360min;
after the grinding reaction is finished, the speed is reduced to continue the slow grinding (the speed is required to achieve the stirring effect, the requirement can be omitted, the subsequent oxidation is prepared), air/oxygen is introduced during the slow grinding to finally oxidize ferrous hydroxide and ferrous carbonate into nano ferric oxide with crystal water, the formed nano ferric oxide is adhered to the surface of nano barium sulfate, and the nano ferric oxide can form a compact coating layer on the surface of nano barium sulfate; in the present invention, the temperature of the polishing slurry is maintained at 20 to 40 ℃ throughout the polishing period. And the slow grinding time is 100min-120min, preferably, the slow grinding speed is: 600-1000r/min. The air/oxygen inlet rate is 2-6L/min.
Then the water-heating reaction kettle is used for removing crystal water after the water-heating treatment at the temperature of 250-300 ℃ and the composite nano transparent iron oxide red is obtained after dehydration and drying. The effect of hydrothermal temperature on particle size is that the higher the temperature the coarser the particles.
The composite nano transparent iron oxide red has a core-shell structure, and is prepared by taking nano ferric oxide as a shell and nano barium sulfate as a core. The nanoscale ferric oxide and barium sulfate particles have larger specific surface areas, so that the nanoscale ferric oxide and barium sulfate particles can be mutually adsorbed; the particle size of the ferric oxide is smaller, so that the nanoscale ferric oxide forms a compact coating layer on the surface of the barium sulfate particles.
Furthermore, in order to facilitate downstream application of the composite nano transparent iron oxide red, the composite nano transparent iron oxide red is subjected to surface modification operation, and the purpose of the modification is to have good affinity with a high-molecular polymer. The object of modification is mainly iron sesquioxide on the outer surface layer. The surface modifier comprises at least one of lauric acid, stearic acid, stearate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, silane, organosilicon and the like.
The modification method comprises the following steps: re-slurrying the composite nano transparent iron oxide red with water, and heating to 60-70 ℃;
coating and modifying stearate, adding the stearate according to 0.2-0.5wt% of the mass of the composite nano transparent iron oxide red, and directly adding and stirring;
coating and modifying the silane, namely adding the silane according to 2-3wt% of the mass of the composite nano transparent iron oxide red after the pH value is regulated to 4-5;
other organic silicon modification such as dimethyl silicone oil can be dry coated, and after high mixing, honeycomb grinding is used.
In addition, in the invention, a catalyst, preferably oxalic acid, can be added into the nano-sander, and the oxalic acid can be decomposed without residue after being calcined later, so that the decomposition is started at 190 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention reacts under grinding: barium carbonate + ferrous sulfate = barium sulfate + ferrous carbonate + ferrous hydroxide and air/oxygen is then introduced to oxidize the ferrous to form ferric oxide. The ferric oxide is attached to the surface of the barium sulfate again to form a compound.
The invention solves the problem of the going of the titanium dioxide byproduct ferrous sulfate, and has the characteristics of easy production, low raw material price, environment-friendly production, no byproduct generation basically, no pollution to the environment and the like. The product has low surface energy after hydrothermal treatment and is easy to disperse, and the composite takes nano barium sulfate as a core to form transparent double oxide iron oxide red; after being organically modified, the modified polymer has good affinity with high molecular polymers, is easy to disperse even if not modified, and can resist high temperature and color change. After modification, the organic matter is decomposed at high temperature, and the use temperature is generally below 300 ℃. The product stability is relatively good, barium sulfate and ferric oxide are compounded to prevent agglomeration, and the barium sulfate can prevent the mutual agglomeration of the ferric oxide.
Drawings
FIG. 1 is a scanning electron microscope photograph of the finished product of example 1.
Fig. 2 is a scanning electron microscope photograph of the finished product of example 2.
Fig. 3 is a scanning electron microscope photograph of the finished product of example 3.
Fig. 4 is a scanning electron microscope photograph of the finished product of example 4.
FIG. 5 is a spectral reflectance of examples 1-4 and comparative examples;
fig. 6 is an external view of the product of example 1.
Detailed Description
The present invention will be further described with reference to the accompanying drawings for a clear and intuitive understanding to those skilled in the art.
Example 1
Mixing 1mol/L ferrous sulfate solution 1L with 1mol/L industrial barium carbonate 1L, uniformly dispersing by a high-speed stirrer, pumping into an experimental nano sand mill by a diaphragm pump, grinding for 180min after the reaction is finished at a speed of 2900r/min, and grinding at a slow speed, wherein the slow grinding speed is as follows: 600r/min, the slow grinding time is 120min; starting to introduce air during the slow grinding period, wherein the air introducing speed is 6L/min; the temperature of the slurry was maintained at 20-40 c throughout the milling period. And (3) after the slurry is discharged, placing the ground slurry in a hydrothermal reaction kettle for carrying out hydrothermal reaction at 250 ℃ for 2 hours, drying to obtain paste, adding water to reslurry the paste into the paste to obtain 10-15wt% of the paste, heating the paste to 60-70 ℃, adding sodium stearate with the mass of 0.2-0.5wt% of the composite nano transparent iron oxide red, carrying out heat preservation and stirring for 30 minutes, dehydrating, and drying at 90 ℃. The finished product was tested for particle size and electron microscopy scan, and the hue and dispersion of the composite nano transparent iron oxide red of example 1 were tested.
Example 2
Mixing 1mol/L ferrous sulfate solution 1L with 1mol/L industrial barium carbonate 1L, uniformly dispersing by a high-speed stirrer, pumping into an experimental nano sand mill by a diaphragm pump, and grinding for 200min at a speed of 2900r/min, wherein the slow grinding is carried out after the reaction is finished, and the slow grinding speed is as follows: 800r/min, and the slow grinding time is 110min; starting to introduce air during the slow grinding period, wherein the air introducing speed is 6L/min; the temperature of the slurry was maintained at 20-40 c throughout the milling period. Discharging the slurry, placing the ground slurry in a hydrothermal reaction kettle for carrying out a hydrothermal reaction at 260 ℃ for 2 hours, drying to obtain a paste, adding water to reslurry the paste into 10-15wt% of the mass number, heating to 60-70 ℃, adding sodium stearate with 0.2-0.5wt% of the mass of the composite nano transparent iron oxide red, carrying out heat preservation and stirring for 30 minutes, dehydrating, and drying at 105 ℃. The finished product is detected to be in particle size and scanned by an electron microscope, and the hue and dispersion of the composite nano transparent iron oxide red in the embodiment 2 are detected.
Example 3
Mixing 1mol/L ferrous sulfate solution 1L with 1mol/L industrial barium carbonate 1L, uniformly dispersing by a high-speed stirrer, pumping into an experimental nano sand mill by a diaphragm pump, grinding for 240min after the reaction is finished at a speed of 2900r/min, and grinding at a slow speed, wherein the slow grinding speed is as follows: 900r/min, and the slow grinding time is 105min; starting to introduce air during the slow grinding period, wherein the air introducing speed is 6L/min; the temperature of the polishing slurry is maintained at 20-40 ℃ during the polishing. After the slurry is discharged, placing the ground slurry into a hydrothermal reaction kettle for hydrothermal reaction at 280 ℃ for 2 hours, drying to obtain paste, adding water to reslurry the paste into 10-15wt% of the mass number, heating to 60-70 ℃, adding sodium stearate with 0.2-0.5wt% of the mass of the composite nano transparent iron oxide red, preserving heat, stirring for 30 minutes, dehydrating, and drying at 105 ℃. The finished product is detected to be in particle size and scanned by an electron microscope, and the hue and dispersion of the composite nano transparent iron oxide red in the embodiment 3 are detected.
Example 4
Mixing 1mol/L ferrous sulfate solution 1L with 1mol/L industrial barium carbonate 1L, uniformly dispersing by a high-speed stirrer, pumping into an experimental nano sand mill by a diaphragm pump, and grinding for 360min at a speed of 2900r/min, wherein the slow grinding is carried out after the reaction is finished, and the slow grinding speed is as follows: 1000r/min, and the slow grinding time is 100min; starting to introduce air during the slow grinding period, wherein the air introducing speed is 6L/min; the temperature of the polishing slurry is maintained at 20-40 ℃ during the polishing. And (3) after the slurry is discharged, placing the ground slurry in a hydrothermal reaction kettle for hydrothermal reaction for 2 hours at 300 ℃, drying to obtain paste, adding water to reslurry the paste into 10-15wt% of the mass, heating to 60-70 ℃, adding sodium stearate with 0.2-0.5wt% of the mass of the composite nano transparent iron oxide red, preserving heat, stirring for 30min, dehydrating, and drying at 105 ℃. The finished product is detected to be in particle size and scanned by an electron microscope, and the hue and dispersion of the composite nano transparent iron oxide red in the embodiment 4 are detected.
The scanning patterns of the electron microscope of the 4 embodiments are shown in fig. 1-4, and in fig. 1-4, dense small particles with rugged shape exist on the surface of the large sphere, which can prove that the products obtained in the embodiments 1-4 are of a composite core-shell structure.
The properties of each example and comparative example are shown in Table 1.
TABLE 1
Description:
l: the positive number indicates white bias and the negative number indicates black bias, indicating the brightness of the color. a: the red-green value is indicated, the positive number indicates reddened, and the negative number indicates greenish. b: indicating a yellow-blue value.
The comparative example was Lang Cheng Touming iron oxide red.
Table 1 shows that the higher the hydrothermal temperature, the higher the conversion of the product, and the better the dispersibility, but the larger the particle size. In addition, the data obtained through the test show that the hue L value of the iron oxide red is improved, the brightness is better, and the red phase is slightly worse than that of the pure iron oxide red of the comparative example.
The spectrum chart shown in fig. 5 can more intuitively compare the comparison effect of each example with that of the comparative example, the red spectrum reflection is mainly between 600 and 740nm, and the reflection spectrum of each example is higher in the spectrum than that of the comparative example in the range of 600 to 740nm, which proves that the color and the luster and the brightness of each example are higher than those of the comparative example.
Compared with the transparent iron oxide red obtained by the traditional method, the iron oxide red synthesized by the method has smaller particle size, higher permeability and lower cost.
Fig. 6 is an external view of the iron oxide red product prepared as represented by example 1, which is a bright red color as seen from the original view.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art, based on the present disclosure, should make improvements and modifications within the scope of the present invention.
Claims (5)
1. The preparation method of the composite nano transparent iron oxide red is characterized by comprising the following steps:
mixing a ferrous sulfate solution and a high-purity barium carbonate solution, grinding by a nano sand mill, and reacting the barium carbonate with the ferrous sulfate to form ferrous carbonate, ferrous hydroxide and barium sulfate under the condition of high-energy collision refinement of the nano sand mill; the grinding speed is 2900r/min, and the grinding time is 180-360min;
after the grinding reaction is finished, the grinding is changed into slow grinding, and air/oxygen is introduced during the slow grinding to oxidize ferrous hydroxide and ferrous carbonate into nano ferric oxide with crystal water, wherein the nano ferric oxide forms a compact coating layer on the surface of nano barium sulfate; the slow grinding speed is 600-1000r/min, and the slow grinding time is 100-120 min; the air/oxygen inlet rate is 2-6L/min;
then carrying out hydrothermal treatment by using a hydrothermal reaction kettle, and dehydrating and drying to obtain composite nano transparent iron oxide red;
wherein the temperature of the polishing slurry is maintained at 20-40 ℃ throughout the polishing period.
2. The method for producing composite nano transparent iron oxide red according to claim 1, wherein the composite nano transparent iron oxide red is further subjected to a surface modification treatment, and the ferric oxide is modified by a surface modifier.
3. The method for manufacturing the composite nano transparent iron oxide red according to claim 2, wherein the surface modifier comprises at least one of lauric acid, stearic acid, stearate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and organic silicon.
4. The method for producing composite nano transparent iron oxide red according to claim 1, wherein the temperature of the hydrothermal reaction vessel is 250-300 ℃.
5. The method for producing composite nano transparent iron oxide red according to claim 1, wherein ferrous sulfate is titanium white byproduct ferrous sulfate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211467028.7A CN115806745B (en) | 2022-11-22 | 2022-11-22 | Composite nano transparent iron oxide red and preparation method thereof |
Applications Claiming Priority (1)
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3582266A (en) * | 1968-09-24 | 1971-06-01 | Merck & Co Inc | Process for producing barium ferrite |
| JP2002146236A (en) * | 2000-11-10 | 2002-05-22 | Mitsui Mining & Smelting Co Ltd | Black pigment and its manufacturing method |
| CN102603009A (en) * | 2012-02-21 | 2012-07-25 | 升华集团德清华源颜料有限公司 | Method for preparing nano transparent ferric oxide red pigment |
| CN102603010A (en) * | 2012-02-21 | 2012-07-25 | 升华集团德清华源颜料有限公司 | Transparent nanometer iron oxide red pigment |
| CN102604435A (en) * | 2012-02-21 | 2012-07-25 | 升华集团德清华源颜料有限公司 | Nano transparent iron oxide yellow pigment |
| CN102616862A (en) * | 2012-02-21 | 2012-08-01 | 升华集团德清华源颜料有限公司 | Method for preparing nano-sized transparent yellow iron oxide pigments |
| CN103663536A (en) * | 2013-09-28 | 2014-03-26 | 赵同甫 | Process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide |
| CN107325588A (en) * | 2017-07-10 | 2017-11-07 | 林中 | A kind of preparation method for the pigment for coating high gorgeous degree iron oxide |
| CN110668485A (en) * | 2018-07-02 | 2020-01-10 | 陈朝华 | Process for preparing barium sulfate and ferrous sulfide from ferrous sulfate and barium sulfide |
| CN113462198A (en) * | 2021-08-12 | 2021-10-01 | 佛山集美精化科技有限公司 | Method for preparing composite titanium dioxide by barium sulfate coprecipitation method |
-
2022
- 2022-11-22 CN CN202211467028.7A patent/CN115806745B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3582266A (en) * | 1968-09-24 | 1971-06-01 | Merck & Co Inc | Process for producing barium ferrite |
| JP2002146236A (en) * | 2000-11-10 | 2002-05-22 | Mitsui Mining & Smelting Co Ltd | Black pigment and its manufacturing method |
| CN102603009A (en) * | 2012-02-21 | 2012-07-25 | 升华集团德清华源颜料有限公司 | Method for preparing nano transparent ferric oxide red pigment |
| CN102603010A (en) * | 2012-02-21 | 2012-07-25 | 升华集团德清华源颜料有限公司 | Transparent nanometer iron oxide red pigment |
| CN102604435A (en) * | 2012-02-21 | 2012-07-25 | 升华集团德清华源颜料有限公司 | Nano transparent iron oxide yellow pigment |
| CN102616862A (en) * | 2012-02-21 | 2012-08-01 | 升华集团德清华源颜料有限公司 | Method for preparing nano-sized transparent yellow iron oxide pigments |
| CN103663536A (en) * | 2013-09-28 | 2014-03-26 | 赵同甫 | Process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide |
| CN107325588A (en) * | 2017-07-10 | 2017-11-07 | 林中 | A kind of preparation method for the pigment for coating high gorgeous degree iron oxide |
| CN110668485A (en) * | 2018-07-02 | 2020-01-10 | 陈朝华 | Process for preparing barium sulfate and ferrous sulfide from ferrous sulfate and barium sulfide |
| CN113462198A (en) * | 2021-08-12 | 2021-10-01 | 佛山集美精化科技有限公司 | Method for preparing composite titanium dioxide by barium sulfate coprecipitation method |
Non-Patent Citations (3)
| Title |
|---|
| 《中学生科学辞典》.《中学生科学辞典》.河南人民出版社,1983,288-290. * |
| 韩长日，宋小平主编.《电子及信息用化学品生产工艺与技术》.科学技术文献出版社,2019,215-220. * |
| 顾翼东主编.《化学词典》.上海辞书出版社,1989,637,1032. * |
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Denomination of invention: A composite nano transparent iron red and its production method Granted publication date: 20230929 Pledgee: Bank of China Limited by Share Ltd. Yunfu branch Pledgor: YUNFU HONGZHI NEW MATERIAL Co.,Ltd. Registration number: Y2024980006093 |