CN109912995B - Method for preparing iron oxide red hybrid pigment with far infrared emission function by using iron tailings - Google Patents
Method for preparing iron oxide red hybrid pigment with far infrared emission function by using iron tailings Download PDFInfo
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Abstract
The invention relates to a method for preparing iron oxide red hybrid pigment with far infrared emission function by using iron tailings. The method comprises the following steps: mixing iron tailings, iron salt and ethanol, and performing ball milling to obtain powder; adding the powder into water to obtain a first suspension, and adding tourmaline nanoparticles after vigorous stirring to obtain a second suspension; and transferring the second suspension into a hydrothermal reaction kettle, reacting for 4-48 h at 140-200 ℃, naturally cooling to room temperature, centrifuging, washing, drying, grinding and sieving to obtain the iron oxide red hybrid pigment with the far infrared emission function. The invention has more green synthetic raw materials and lower preparation cost, and opens up a new way for the resource and high-added-value functional utilization of iron tailings which are abundant in reserves and are urgently to be utilized in China.
Description
Technical Field
The invention relates to a preparation method of an iron oxide red hybrid pigment with a far infrared emission function, in particular to a method for preparing the iron oxide red hybrid pigment with the far infrared emission function by using iron tailings, belonging to the technical field of iron tailing deep processing and nano composite material preparation.
Background
The iron oxide red pigment is a common inorganic pigment, has high covering power and tinting strength, is green and safe, and is widely used in the fields of coatings, building materials, plastics, ceramics, rubber and the like. In recent years, with the enhancement of energy saving and environmental protection consciousness, the coating with far infrared emission performance attracts more and more attention, especially has strong radiance (C: (R))>0.9) and corrosion resistance. The iron tailings are the main component of industrial solid waste and are made of SiO2、Al2O3、Fe2O3CaO, MgO, etc. as main components, and gangue minerals such as quartz, chlorite, amphibole, feldspar, pyroxene, etc. as main phases. Studies have shown that iron (Fe) trioxide2O3) And silicon dioxide (SiO)2) Is a good raw material for producing high far infrared radiation material (Japanese patent JP127349[ P ]](ii) a The scientific report of the silicate salt is provided,1997,25(1):24), and Al2O3Can further improve SiO2The iron tailings have the advantage of preparing the iron red hybrid pigment with the far infrared emission function.
Furthermore, the iron element contained in the iron tailings is expected to be used as the main phase alpha-Fe of iron source synthetic iron red pigment2O3Aluminum element is expected to improve the vividness and thermal stability of iron oxide red, and abundant silicon element is expected to provide a carrier for iron oxide red pigment and improve the red color thereof (ceram. int.34(2008) 49; ACS. mater. inter.6(2014) 20282). However, because the components of the iron tailings are complex in composition and the interaction mechanism of the components is complex, a plurality of technical points need to be researched and overcome in specific application. At present, the research and utilization of the iron tailings are mainly aimed at environmental protection, and no report is provided for constructing a high value-added functional material according to the natural silicate composite mineral natural characteristics of the iron tailings.
In addition, tourmaline is a silicate mineral having a cyclic structure of aluminum, sodium, iron, magnesium, and lithium, which is characterized by containing boron. The crystal is in c-axis three-fold symmetry in space, and has no symmetry center perpendicular to the c axis. Because of the special crystal structure, the tourmaline has special performances of piezoelectric effect, thermoelectric effect, spontaneous polarization, far infrared emission and the like. Liujie et al (J Nanosci Nanotechno,2016,16(4):377) have found that ceramic materials having far infrared emission properties can be prepared using natural tourmaline minerals. However, the research on the far infrared emission performance of the tourmaline-reinforced material is just started, and the report of reinforcing the far infrared emission performance of the iron red pigment by using tourmaline is not found yet.
Disclosure of Invention
The invention aims to provide a method for preparing an iron oxide red hybrid pigment with a far infrared emission function by using iron tailings aiming at the defects existing in the current research and utilization of the iron tailings. The method selects industrial solid waste iron tailings as raw materials, natural mineral tourmaline as an additive, and synthesizes the functional iron oxide red hybrid pigment through proper proportion and parameters. The invention has more green synthetic raw materials and lower preparation cost, and opens up a new way for the resource and high-added-value functional utilization of iron tailings which are abundant in reserves and are urgently to be utilized in China.
The technical scheme of the invention is as follows:
a method for preparing iron oxide red hybrid pigment with far infrared emission function by using iron tailings comprises the following steps:
mixing iron tailings, iron salt and a certain amount of ethanol into paste, transferring the paste into a ball mill, performing ball milling for 1-3 h to obtain dry powder, and screening the dry powder through a 400-mesh screen to obtain powder; adding the powder into water to obtain a first suspension, stirring, performing ultrasonic dispersion, adding alkali, violently stirring for 30-60 min to completely dissolve the alkali, then adding tourmaline nanoparticles, and continuously stirring and performing ultrasonic treatment for 1-4 h respectively to obtain a second suspension; and transferring the second suspension into a hydrothermal reaction kettle, reacting for 4-48 h at 140-200 ℃, naturally cooling to room temperature, centrifuging, washing, drying, grinding and sieving to obtain the iron oxide red hybrid pigment with the far infrared emission function.
Wherein 0.375-1.5 mol of iron salt and 40-70 mL of ethanol are added into each 100g of iron tailings; the mass of the powder is 1-10% of that of the first suspension; the molar weight of the alkali is 1-4 times of that of the ferric salt; the mass of the tourmaline nano-particles is 0.01-2% of that of the iron tailings.
SiO of the iron tailings240-65% of Al2O3、Fe2O3The amount of each is 10 to 20 percent.
The tourmaline is one or two of iron tourmaline and magnesium tourmaline.
The iron salt is one or more of ferric chloride, ferric sulfate and ferric nitrate.
The alkali is one or more of hexamethylenetetramine, ammonia water, urea, sodium metasilicate, sodium hydroxide and sodium carbonate.
The violent stirring is carried out at a stirring speed of 4000-5500 r/min.
The invention has the beneficial effects that:
the invention discloses a method for preparing an iron oxide red hybrid pigment with a far infrared emission function by taking iron tailings as a raw material and tourmaline as an additive and adopting a hydrothermal reaction, wherein the hybrid pigment is bright red, has a maximum a value of 36.1 and a maximum far infrared emissivity of 0.96, and is expected to be applied to multiple fields of coatings, paints, ceramics, printing inks, coatings and the like. The invention can provide a new strategy for the preparation of the functional iron oxide red pigment, reduce the synthesis cost of the functional iron oxide red pigment, and open up a new way for the resource utilization and high-added-value functional utilization of iron tailings which are abundant in reserves and are urgently to be utilized in China.
Drawings
FIG. 1 is a TEM photograph of a bright red iron red hybrid pigment prepared in example 1, wherein FIG. 1a is a TEM photograph of a single pigment particle; FIG. 1b is a partial magnified view of a TEM photograph of a single pigment particle;
FIG. 2 is an XRD spectrum of a bright red iron red hybrid pigment prepared in example 1;
FIG. 3 shows the IR emissivity, chemical composition and chromaticity values of the bright red iron red hybrid pigment prepared in example 1.
Detailed Description
The technical solution of the invention is further illustrated below with reference to examples, which are not to be construed as limiting the technical solution.
The iron tailings are particularly Hebei province 28390, Heping iron tailings and SiO thereof240-65% of Al2O3、Fe2O3The amount of the main phase is 10-20 percent respectively, the main phase is quartz, hydrated calcium aluminate, albite and muscovite, and the grain diameter is 75 mu m.
The tourmaline is specifically Hebei pacified paraferrotourmaline, and the particle size is 100-350 nm.
Example 1: mixing 2.0g of iron tailing powder, 0.022mol of ferric chloride and 1.2mL of ethanol into paste, transferring the paste into a ball mill for ball milling for 1h, then screening all the obtained dry powder through a 400-mesh screen, dispersing the dry powder in 60mL of deionized water, fully stirring (3500r/min, 2h) and ultrasonically dispersing (1h), adding 2g of sodium hydroxide and 1mL of ammonia water (mass fraction of ammonia water: 28 wt%; total alkali molar quantity: 0.0648mol), violently stirring at the rotating speed of 4500r/min for 30min, adding 0.01g of tourmaline powder, continuously stirring (3000r/min) and ultrasonically treating for 1h to obtain uniform suspension, transferring the suspension into a hydrothermal reaction kettle, reacting for 24h under the condition of 160 ℃, naturally cooling to room temperature, centrifuging, washing, drying, grinding, and screening through a 300-mesh screen to obtain the bright red iron red hybrid pigment with far infrared emission performance.
The obtained pigment has a particle size of 260nm and a shape of ellipsoid with protrusions, wherein the ellipsoid is composed of spherical particles (shown in FIG. 1); the main phase components are muscovite, albite, ferric oxide and quartz (as shown in figure 2); the infrared emissivity is up to 0.92 (infrared wavelength: 10-20 μm), the red color a is up to 35.45, the brightness value L is 42.53, and the main chemical component is Fe2O3、SiO2、Al2O3And a small amount of Na2O (as shown in fig. 3). (the infrared emissivity is tested by a German Bruker 8000-10/0.18 Fourier transform infrared spectrometer; the chromaticity is tested by CR-400/410 of Beijing Ke Meirunda instruments and equipments Co., Ltd.)
Example 2: mixing 3.0g of iron tailing powder, 0.055mol of ferric chloride and 1.5mL of ethanol into paste, transferring the paste into a ball mill, carrying out ball milling for 1.5h, then screening all the obtained dry powder through a 400-mesh screen, dispersing the dry powder in deionized water, fully stirring (3500r/min, 2h) and ultrasonic (30min), adding 5mL of ammonia water (mass fraction of ammonia water: 28 wt.%), 2g of sodium metasilicate (total alkali molar quantity: 0.0845mol), violently stirring at the rotating speed of 5000r/min for 30min, then adding 0.005g of tourmaline powder, continuously stirring (2000r/min, 2h) and ultrasonic (1h) to obtain uniform suspension, transferring the suspension into a hydrothermal reaction kettle, reacting for 12h under the condition of 180 ℃, naturally cooling to room temperature, centrifuging, washing, drying, grinding and screening through a 300-mesh screen to obtain the bright red iron red hybrid pigment with far infrared emission performance.
The pigment has a particle size of 180nm, an infrared emissivity of up to 0.91 (infrared wavelength: 10-20 μm), a red phase a of up to 34.49, and a brightness value L of 44.51 (infrared emissivity measured by Bruker 8000-10/0.18 Fourier transform infrared spectrometer, Germany; chroma measured by CR-400/410, Beijing Korea Mitsumada instruments and equipments Co., Ltd.).
Example 3: mixing 4.0g of iron tailing powder, 0.048mol of ferric chloride and 2.0mL of ethanol into paste, transferring the paste into a ball mill for ball milling for 2.5h, screening the obtained dry powder with a 400-mesh screen, dispersing the dry powder in deionized water, fully stirring (3500r/min, 2h) and ultrasonic (1h), adding 4g of sodium hydroxide and 2g of hexamethylenetetramine (total alkali molar weight: 0.114mol), violently stirring at the rotating speed of 4800r/min for 45min, adding 0.0025g of tourmaline powder, continuously stirring (2000r/min) and ultrasonic for 2h to obtain uniform suspension, transferring the suspension into a hydrothermal reaction kettle, reacting for 48h at the temperature of 140 ℃, naturally cooling to room temperature, centrifuging, washing, drying, grinding, and screening with a 300-mesh screen to obtain the bright red iron red hybrid pigment with far infrared emission performance.
The obtained pigment has a particle size of 150nm, an infrared emissivity of up to 0.90 (infrared wavelength: 10-20 μm), a red phase a of up to 32.11, and a brightness value L of 44.92 (infrared emissivity measured by Bruker 8000-10/0.18 Fourier transform infrared spectrometer, Germany; chroma measured by CR-400/410, Beijing Korea Mitsumada instruments and equipments Co., Ltd.).
Example 4: mixing 1.5g of iron tailing powder, 0.022mol of ferric chloride and 1.0mL of ethanol into paste, transferring the paste into a ball mill for ball milling for 1.5h, screening the obtained dry powder with a 400-mesh screen, dispersing the powder in deionized water, fully stirring (3500r/min, 1h) and performing ultrasound (30min), adding 2mL of ammonia (the mass fraction of ammonia: 28 wt.%), 1.5g of sodium carbonate (the molar quantity of total alkali: 0.0438mol), violently stirring for 45min at the rotating speed of 4000r/min, adding 0.0015g of tourmaline powder, continuously stirring (3500r/min) and performing ultrasound for 1h to obtain uniform suspension, transferring the suspension into a hydrothermal reaction kettle, reacting for 6h at the temperature of 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying, grinding and screening with a 300-mesh screen to obtain the bright red iron red hybrid pigment with far infrared emission performance.
The obtained pigment has a particle size of 100nm, an infrared emissivity of up to 0.93 (infrared wavelength: 10-20 μm), a red phase a of up to 35.29, and a brightness value L of 43.15 (infrared emissivity measured by Bruker 8000-10/0.18 Fourier transform infrared spectrometer, Germany, and chromaticity measured by CR-400/410, Beijing Cor Miudan instruments and equipments Co., Ltd.).
Example 5: mixing 6.0g of iron tailing powder, 0.074mol of ferric chloride and 3.5mL of ethanol into paste, transferring the paste into a ball mill for ball milling for 3.0h, screening the obtained dry powder with a 400-mesh screen, dispersing the dry powder in deionized water, fully stirring (3500r/min, 2h) and ultrasonic (2h), adding 12g of urea and 1.5g of sodium hydroxide (total alkali molar weight: 0.238mol), violently stirring at a rotating speed of 5500r/min for 60min, adding 0.5g of tourmaline powder, continuously stirring (1500r/min) and ultrasonic for 2h to obtain uniform suspension, transferring the suspension into a hydrothermal reaction kettle, reacting for 36h at 180 ℃, naturally cooling to room temperature, centrifuging, washing, drying, grinding and screening with a 300-mesh screen to obtain the bright red iron red hybrid pigment with far infrared emission performance.
The obtained pigment has a particle size of 220nm, an infrared emissivity of up to 0.94 (infrared wavelength: 10-20 μm), a red phase a of up to 32.11, and a brightness value L of 42.15 (infrared emissivity measured by Bruker 8000-10/0.18 Fourier transform infrared spectrometer, Germany; chroma measured by CR-400/410, Beijing Korea Mitsumada instruments and equipments Co., Ltd.).
The invention is not the best known technology.
Claims (2)
1. A method for preparing iron oxide red hybrid pigment with far infrared emission function by using iron tailings is characterized by comprising the following steps:
mixing iron tailings, iron salt and a certain amount of ethanol into paste, transferring the paste into a ball mill, performing ball milling for 1-3 h to obtain dry powder, and screening the dry powder through a 400-mesh screen to obtain powder; adding the powder into water to obtain a first suspension, stirring, performing ultrasonic dispersion, adding alkali, vigorously stirring for 30-60 min to completely dissolve the alkali, then adding tourmaline nanoparticles, and continuously stirring and performing ultrasonic treatment for 2-4 h to obtain a second suspension; transferring the second suspension into a hydrothermal reaction kettle, reacting for 4-48 h at 140-200 ℃, naturally cooling to room temperature, centrifuging, washing, drying, grinding and sieving to obtain the iron oxide red hybrid pigment with the far infrared emission function;
wherein 0.375-1.5 mol of iron salt and 40-70 mL of ethanol are added into each 100g of iron tailings; the mass of the powder is 1-10% of that of the first suspension; the molar weight of the alkali is 1-4 times of that of the ferric salt; the mass of the tourmaline nano-particles is 0.01-2% of that of the iron tailings.
SiO of the iron tailings240-65% of Al2O3、Fe2O3Respectively of10 to 20 percent;
the tourmaline is one or two of iron tourmaline and magnesium tourmaline;
the ferric salt is one or more of ferric chloride, ferric sulfate and ferric nitrate;
the alkali is one or more of hexamethylenetetramine, ammonia water, urea, sodium metasilicate, sodium hydroxide and sodium carbonate.
2. The method for preparing iron-red hybrid pigment with far infrared emission function by using iron tailings as claimed in claim 1, wherein the vigorous stirring is 4000-5500 r/min.
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