CN109810546A - The method for preparing shiny red iron oxide red hybrid pigment using iron tailings - Google Patents
The method for preparing shiny red iron oxide red hybrid pigment using iron tailings Download PDFInfo
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- CN109810546A CN109810546A CN201910269525.8A CN201910269525A CN109810546A CN 109810546 A CN109810546 A CN 109810546A CN 201910269525 A CN201910269525 A CN 201910269525A CN 109810546 A CN109810546 A CN 109810546A
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Abstract
The present invention is a kind of method for preparing shiny red iron oxide red hybrid pigment using iron tailings.Method includes the following steps: iron tailings powder is added in iron salt solutions, add alkali, after being vigorously stirred 20~40min, continue stirring and each 30min~4h of ultrasound obtains suspension, the suspension is gone in hydrothermal reaction kettle, 4~48h is reacted under the conditions of 140~200 DEG C, obtains shiny red iron oxide red hybrid pigment.Iron tailings is treated as the utilization of resources by the present invention, both environment and energy problem can be solved, again new way can be provided to reduce the preparation cost of iron oxide red pigment, synthesis path is more green, preparation cost is less expensive, utilizes for China's rich reserves, the recycling of the iron tailings urgently utilized, high added value functionalization and opens up new way.
Description
Technical field
The present invention relates to a kind of preparation methods of shiny red iron oxide red hybrid pigment more particularly to a kind of utilization iron tailings to prepare
The method of shiny red iron oxide red hybrid pigment, belongs to iron tailings deep processing and nanocomposite preparation technical field.
Background technique
Iron tailings is the chief component of industrial solid castoff, as one kind two due to valuable material rich in
Secondary resource is by world's extensive concern.And currently, the comprehensive utilization ratio of China's iron tailings only has 7%, the iron tailings amount of stockpiling is up to
Several hundred billion tons.The waste that resource is not only resulted in using difficulty of iron tailings, also brings many serious environmental problems, seriously
Deteriorate the air environment and water environment of surrounding area.To realize having for economy of resources, economic benefit, social benefit and environmental benefit
Effect is unified, utilizes to iron tailings recycling, high added value functionalization most important.
Iron oxide red pigment is a kind of common inorganic pigment, and main component is α-Fe2O3, there is very high covering power and coloring
Power, and it is green safe, it is widely used in the fields such as coating, building materials, plastics, ceramics and rubber.But the color of iron oxide red pigment is general
It is more dim, it is lackluster, it is difficult to compare favourably with the red pigment containing toxic heavy metal ion, limits it in high-end product
In application.In recent years, researcher has found that the presence of silicon matrix has the red phase (Ceram.Int.34 for being conducive to improve iron oxide red
(2008) 491), the presence of aluminium element can make its color more bright-coloured and high temperature resistant (ACS Appl.Mater.Inter.6 (2014)
20282).Tian etc. (Ceram.Int.43 (2017) 1862) has found the natural silicate clay mine containing silicon skeleton and aluminium element
The coloration and thermal stability of iron oxide red pigment can be significantly improved.
China's iron tailings is with SiO2、Al2O3、Fe2O3, CaO, MgO etc. be main component, with quartz, chlorite, hornblend,
The gangue quartzs mineral such as feldspar, pyroxene are main object phase.These mineral element silicon all rich in, basic unit all include
[SiO4] tetrahedron, carrier can be provided for iron oxide red pigment and improve its red phase.Moreover, iron tailings typically contains aluminium member abundant
Element and ferro element, ferro element can be used as source of iron synthesis α-Fe2O3, and aluminium element can be used to improve the vividness and thermostabilization of iron oxide red
Property.Opposite natural silicate clay mineral, iron tailings have the characteristics that volume of cargo in storage it is big, it is low in cost, need utilization.But due to iron
Tailing ingredient complicated composition, the mutual mechanism of action situation of component is complicated, causes in its concrete application, there is also many technologies to want
Point needs to study and overcome.The research and utilization of iron tailings is mostly for the purpose of environmental protection at present, still without the natural silicon for iron tailings
Hydrochlorate complex mineral natural endowment characteristic constructs the report of high added value functional material.
Summary of the invention
The purpose of the present invention is for deficiency present in current techniques, provide a kind of utilization iron tailings to prepare shiny red iron
The method of red hybrid pigment.It is raw material by suitable proportion and parameter that this method, which selects industrial solid castoff iron tailings, is closed
At iron oxide red hybrid pigment.Iron tailings is treated as the utilization of resources by the present invention, can not only solve environment and energy problem, but also can be reduction iron
The preparation cost of red pigment provides new way, and synthesis path is more green, preparation cost is less expensive, for China's rich reserves, urgently
Recycling, the high added value functionalization of the iron tailings utilized, which utilize, opens up new way.
Technical solution of the invention:
A method of shiny red iron oxide red hybrid pigment being prepared using iron tailings, method includes the following steps:
Iron tailings powder is added in iron salt solutions, alkali is added after stirring, ultrasound, after being vigorously stirred 20~40min, after
Continuous stirring and each 30min~4h of ultrasound, obtain suspension, which are gone in hydrothermal reaction kettle, 140~200 DEG C of conditions
4~48h of lower reaction, after cooled to room temperature, centrifugation, washing, it is dry, be ground up, sieved to obtain shiny red iron oxide red hybrid pigment；
Wherein, every gram of iron tailings powder is added in 10~60mL iron salt solutions；The mole of alkali is the 1 of molysite mole
~4 times.
The SiO of the iron tailings2Content is 35~65%, Al2O3、Fe2O3Amount be respectively 8~15%.
The molysite is one or both of iron chloride, ferric sulfate and ferric nitrate.
The alkali is hexamethylenetetramine, ammonium hydroxide, urea, sodium metasilicate, sodium hydroxide, sodium carbonate, sodium salicylate and ten
One of dialkyl dimethyl glycine betaine is a variety of.
The concentration of the iron salt solutions is 0.2~1.5mol/L.
Described being vigorously stirred as revolving speed is 4000~5500r/min.
The beneficial effects of the present invention are:
Iron tailings is changed into shiny red iron oxide red hybrid pigment by hydro-thermal reaction by the present invention, and the L* value of the hybrid pigment is
43.1, a* value is 37.9, b* value is 23.7, and shows good high thermal stability, is still kept through 1200 DEG C of calcining 4h processing
Beautiful red, calcined chromatic value L*, a*, b* are respectively 39.1,30.1,20.9, be expected to be applied to coating, paint, ceramics,
The multiple fields such as ink, coating.The present invention can provide new method to improve the coloration of iron oxide red pigment, reducing its synthesis cost, be
China's rich reserves, the recycling of the iron tailings urgently utilized, high added value functionalization, which utilize, opens up new way.
Detailed description of the invention
Fig. 1 is the XRD spectra that iron tailings, embodiment 1 prepare shiny red iron oxide red hybrid pigment.
Fig. 2 is the SEM photograph that iron tailings, embodiment 1 prepare shiny red iron oxide red hybrid pigment, wherein Fig. 2 a is iron tailings
SEM photograph, Fig. 2 b be preparation shiny red iron oxide red hybrid pigment SEM photograph.
Fig. 3 is that embodiment 1 prepares chromatic value of the shiny red iron oxide red hybrid pigment through 1100 DEG C of calcining front and backs.
Specific embodiment
Technical solution of the invention is described further below with reference to embodiment, these embodiments should not be understood as
It is the limitation to technical solution.
The iron tailings is specially Rocks in Luanping, Hebei Province iron tailings, SiO2Content is 35~65%, Al2O3、Fe2O3Amount point
Not Wei 8~15%, main object is mutually quartz, calcium aluminate hydrates, albite, muscovite, and pattern is more complex, including lamella knot
Structure, nutty structure and irregular block structure, partial size are 50 μm or so.
Embodiment 1: the water that 60mL concentration is 0.37mol/L iron chloride is dispersed by the iron tailings powder of 2.0g ball-milling treatment
(2500r/min, 2h) and ultrasonic (30min) in solution, is sufficiently stirred, 1g sodium hydroxide, 1mL ammonium hydroxide (ammonium hydroxide quality point are added afterwards
Number: 28wt.%；Total alkali mole: 0.0398mol), after being vigorously stirred 30min with the revolving speed of 4800r/min, continue to stir
(1500r/min) and each 2h of ultrasound obtain uniform suspension, which is gone in hydrothermal reaction kettle, is reacted under the conditions of 160 DEG C
For 24 hours, after cooled to room temperature, centrifugation, drying, is ground up, sieved to obtain shiny red iron oxide red hybrid pigment washing.
The main object phase composition for obtaining iron oxide red pigment is α-Fe2O3, albite, quartz (as shown in Figure 1)；Pattern is relatively regular,
For class silk cocoon pattern, partial size is 160nm (as shown in Figure 2)；It is that 21.1, L* value is up to 42.1 that a* value, which is up to 37.7, b* value, explanation
Its color is beautiful, and chromatic value is basically unchanged after 1100 DEG C of calcinings, illustrates that gained pigment has good heat resistance (such as Fig. 3 institute
Show) (coloration is tested by the CR-400/410 of Beijing section U.S. profit up to experimental instruments and equipment limited).
Embodiment 2: dispersing 60mL concentration for the iron tailings powder of 4.0g is 0.18mol/L iron chloride, 0.21mol/L sulphur
In the aqueous solution of sour iron, be sufficiently stirred (3000r/min, 2h) and ultrasonic (1.5h) be added afterwards 6mL ammonium hydroxide (ammonium hydroxide mass fraction:
28wt.%；Mole: 0.0888mol), it is vigorously stirred after 30min with the revolving speed of 4500r/min and continues to stir (1500r/min)
Uniform suspension is obtained with each 1h of ultrasound, which is gone in hydrothermal reaction kettle, 12h, natural cooling are reacted under the conditions of 180 DEG C
To room temperature, centrifugation, drying, is ground up, sieved to obtain shiny red iron oxide red hybrid pigment washing, and partial size 210nm, a* value are high
Up to 35.9, b* value be 22.1, L* value be up to 44.2, illustrate its color it is beautiful (coloration by Beijing section U.S. profit up to instrument and equipment it is limited
The CR-400/410 of company is tested).
Embodiment 3: dispersing the iron tailings powder of 3.0g in the aqueous solution that 60mL concentration is 0.74mol/L ferric nitrate,
(2000r/min, 1h) and ultrasonic (1.5h) is sufficiently stirred, 3mL ammonium hydroxide (ammonium hydroxide mass fraction: 28wt.%), the inclined silicon of 3g are added afterwards
Sour sodium (total alkali mole: 0.0602mol) is vigorously stirred after 30min with the revolving speed of 5000r/min and continues to stir (2000r/
Min, 2h) and ultrasonic (30min) uniform suspension, which is gone in hydrothermal reaction kettle, is reacted under the conditions of 200 DEG C
6h, after cooled to room temperature, centrifugation, washing, it is dry, be ground up, sieved to obtain shiny red iron oxide red hybrid pigment, partial size is
190nm, a* value be up to 33.9, b* value be 23.2, L* value be up to 42.7, illustrate its color it is beautiful (coloration by Beijing section U.S. profit reaches
The CR-400/410 of experimental instruments and equipment limited is tested).
Embodiment 4: dispersing the iron tailings powder of 1.5g in the aqueous solution that 60mL concentration is 0.27mol/L ferric sulfate,
Be sufficiently stirred (3500r/min, 1h) and ultrasonic (30min) be added afterwards 1.5g sodium metasilicate, 0.5g urea (total alkali mole:
0.0162mol), it is vigorously stirred after 30min with the revolving speed of 5500r/min and continues to stir (2500r/min) and ultrasonic each 2h is obtained
One suspension goes to the suspension in hydrothermal reaction kettle, reacts 48h under the conditions of 140 DEG C, after cooled to room temperature, centrifugation,
Washing, is ground up, sieved to obtain shiny red iron oxide red hybrid pigment drying, and partial size 150nm, a* value is up to 36.7, b* value and is
21.6, L* value is up to 42.9, illustrates beautiful (CR-400/ of the coloration by Beijing section U.S. profit up to experimental instruments and equipment limited of its color
410 tests).
Embodiment 5: it disperses the iron tailings powder of 6.0g in the aqueous solution that 60mL concentration is 1.2mol/L ferric sulfate, fills
3.5g dodecyldimethylammonium hydroxide inner salt, 0.9g sodium salicylate, 10.8g is added after dividing stirring (2500r/min) and each 2h of ultrasound
Sodium hydroxide (total alkali mole: 0.287mol) is vigorously stirred after 30min with the revolving speed of 4000r/min and continues to stir (2000r/
Min) and each 1.5h of ultrasound obtains uniform suspension, which is gone in hydrothermal reaction kettle, reacts 48h under the conditions of 180 DEG C, from
After being so cooled to room temperature, centrifugation, washing, it is dry, be ground up, sieved to obtain shiny red iron oxide red hybrid pigment, partial size 195nm,
It is that 23.8, L* value is up to 41.2 that a* value, which is up to 31.7, b* value, illustrates that beautiful (coloration is moistened by Beijing section beauty to be set up to instrument its color
The CR-400/410 of standby Co., Ltd is tested).Unaccomplished matter of the present invention is well-known technique.
Claims (5)
1. a kind of method for preparing shiny red iron oxide red hybrid pigment using iron tailings, it is characterized in that method includes the following steps:
Iron tailings powder is added in iron salt solutions, alkali is added after stirring, ultrasound, after being vigorously stirred 20 ~ 40 min, continues to stir
Each h of 30 min ~ 4 of ultrasound is mixed and stirred, suspension is obtained, which is gone in hydrothermal reaction kettle, it is anti-under the conditions of 140 ~ 200 DEG C
Answer 4 ~ 48 h, after cooled to room temperature, centrifugation, washing, it is dry, be ground up, sieved to obtain shiny red iron oxide red hybrid pigment；
Wherein, every gram of iron tailings powder is added in 10 ~ 60 mL iron salt solutions；The mole of alkali is the 1 ~ 4 of molysite mole
Times；
The concentration of the iron salt solutions is 0.2 ~ 1.5 mol/L.
2. the method for preparing shiny red iron oxide red hybrid pigment using iron tailings as described in claim 1, it is characterized in that the iron
The SiO of tailing2Content is 35 ~ 65%, Al2O3、Fe2O3Content be respectively 8 ~ 15%.
3. the method for preparing shiny red iron oxide red hybrid pigment using iron tailings as described in claim 1, it is characterized in that described
Molysite is one or both of iron chloride, ferric sulfate and ferric nitrate.
4. the method for preparing shiny red iron oxide red hybrid pigment using iron tailings as described in claim 1, it is characterized in that the alkali
For hexamethylenetetramine, ammonium hydroxide, urea, sodium metasilicate, sodium hydroxide, sodium carbonate, sodium salicylate and dodecyl dimethyl sweet tea
One of dish alkali is a variety of.
5. the method for preparing shiny red iron oxide red hybrid pigment using iron tailings as described in claim 1, it is characterized in that described
It is vigorously stirred as 4000 ~ 5500 r/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111334089A (en) * | 2020-01-08 | 2020-06-26 | 杨学棒 | Weathering ceramic paint pigment containing meteorite mineral and using method thereof |
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