CN1226354C - Composite gaolinite/rare-earth/iron oxide-base nano pigment and its microwave process for synthesizing it - Google Patents
Composite gaolinite/rare-earth/iron oxide-base nano pigment and its microwave process for synthesizing it Download PDFInfo
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- CN1226354C CN1226354C CN 01130133 CN01130133A CN1226354C CN 1226354 C CN1226354 C CN 1226354C CN 01130133 CN01130133 CN 01130133 CN 01130133 A CN01130133 A CN 01130133A CN 1226354 C CN1226354 C CN 1226354C
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- iron
- rare earth
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- kaolin
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Abstract
The present invention relates to a kaolin / rare earth / ferric oxide based composite new pigment and a microwave energy saving synthesis method thereof. In the method, ferrous sulfate heptahydrate is used as major raw materials; oxidation is promoted by trace quantity rare earth; nanometer level composite ferrite yellow, ferric oxide red and ferric oxide black can be respectively manufactured by three-section microwave heat treatment; the average particle diameter is from 40 nm to 100 nm. The product has light resistance, corrosion resistance, high chemical stability, no poisonous drugs, high transparence, good dispersiveness, bright color and low cost; besides, the raw materials are easy to obtain; the product has multitude advantages which are difficult to be replaced by other colors. The product can be used as a high-grade ferric series pigment of high-grade car paint, architectural paint, anti-corrosion paint, powdery paint, high-grade printing ink, cosmetics of beauty treatment, fiber products, plastic, household appliances, ceramic, building industries, etc.
Description
Technical field
The present invention relates to kaolin/rare earth/iron oxide yellow, iron oxide red and iron black nano combined new pigment and the quick synthesis method of microwave energy saving thereof.
Background technology
Iron system (base) pigment is one of most important inorganic color(ed)pigment, and its annual production occupies the output that surpasses titanium dioxide first of the inorganic color(ed)pigment.Traditional iron oxide pigment production adopts sulfuric acid process usually, promptly uses metal iron filings and denseer sulfuric acid, under long-time heating is boiled condition, makes through the two-step oxidation method.This method production operation is extensive, and quality product is of low grade, can only produce medium-sized product.All there is bigger gap in China aspect production level and the production kind, has seriously restricted the preparation and the application of iron pigment.In addition, exist the industrial effluent amount big in the production process, remaining sulfur waste acidacidity height directly discharges problems such as meeting serious environment pollution.
Ultra micro (carefully) particle is a kind of transition state between atom, molecule and macroscopical bulk matter, because there is the special property that is different from block materials of many excellences in it at aspects such as light, chemically reactives, the acquisition of ultramicron has huge Practical significance.The traditional industry method for making of ultra-fine transparent iron oxide pigment mainly contains air oxidation process, sodium chlorate oxidation style and iron carbonyl oxidation style.The above two are raw material with ferrous sulfate and caustic soda all, but the oxygenant difference that is adopted, it is raw material that the latter adopts expensive iron carbonyl, makes product through high-temperature calcination.The disadvantage of aforesaid method is the synthesis technique complexity, the production cost height.
Summary of the invention
The object of the invention is to provide a kind of composite pigment and preparation method thereof, this pigment is nontoxic, tasteless, have good heat-resisting, weather-proof, acid-alkali-corrosive-resisting ability, and have excellent specific properties such as colored bright-coloured, strong coloring force, transparency height and strong absorption ultraviolet ray, its preparation method preparation technology is simple, easy to operate, productive rate height, efficient energy-saving.
The nano oxidized iron-based composite pigment of the present invention includes rare earth oxide, ferric oxide, and the shared weight percent of each component is:
Rare earth oxide 0.01～1.2%
Ferric oxide 50～98.8%.
This composite pigment also includes kaolin, and shared weight percent is 0～49%.
The preparation method of nano oxidized iron-based composite pigment is, earlier iron vitriol is mixed with rare-earth salts or rare earth oxide before reaction, or adds kaolin simultaneously and be mixed, water is deployed into slurry then, carry out microwave heating treatment again, make the compound new pigment of required nano oxidized iron-based; Feed intake and be by weight: iron vitriol 10～15, rare-earth salts or rare earth oxide 0.01～0.5, kaolin 0～10.Employed rare-earth salts or rare earth oxide are rare earth oxalate salt or rare earth oxide.Employed kaolin is that chemical constitution is Al
2O
32SiO
22H
2O, crystal formation are the kaolin of sheet structure.
When microwave heating treatment power is 160～480W, the time is 15～35min, makes nano iron oxide yellow.
When microwave heating treatment power is 320～720W, the time is 9～18min, makes nanometer iron oxide red.
When microwave heating treatment power is 720～800W, the time is 9～19min, makes nano-sized black iron oxide.
When nano iron oxide yellow, best microwave generated time is 30min.
The present invention is by product (industrial residue)-iron vitriol (FeSO that adopts the titanium powder plant cheapness
4.7H
2O) make main raw material.Main composition through this law synthetic target product is iron oxide yellow FeO (OH), red iron oxide (Fe
2O
3) and iron oxide black (FeO.Fe
2O
3).
The present invention uses rare earth element as the pigment functionalized in microwave chemical reaction is synthetic, in the pigment prepared process, can accelerate Fe widely
2+→ Fe
3+Oxidizing reaction speed, they have the oxidation of urgency and micritization and spheroidization effect simultaneously.Used rare earth element is nitrate, oxalate and the muriate of any or they in light rare earths oxide compound (as lanthanum trioxide, cerium oxide, Neodymium trioxide), middle-weight rare earths oxide compound (Samarium trioxide, europium sesquioxide, gadolinium sesquioxide) and the heavy rare-earth oxide (Erbium trioxide, ytterbium oxide, yttrium oxide).
The present invention adopts kaolin as additive in the nano combined pigment prepared process of iron-based, and used kaolin chemistry consists of Al
2O
32SiO
22H
2O becomes alukalin after microwave thermal is handled, its sial chemical composition is constant.Kaolin is also referred to as " china clay ", is the distinctive a kind of natural nonmetal mineral of China.Add the kaolin collaborative dissemination that both can combine, can exempt the use tensio-active agent, also can make title thing color need arbitrarily to allocate, and can further reduce production costs by the depth with rare earth ion.
The present invention adopts three sections microwaves to synthesize target compound, compare with the conventional high-temperature solid phase synthesis, reaction times can shorten tens times, intermediate product is few, the micritization effect is stronger, so can make the product (see Table 1 and accompanying drawing FE-SEM field emission scanning electron microscope figure) of the good dispersion degree about median size tens nanometers to one hundred nanometers.Experimental results show that, the microwave reaction time can be regulated and control by different product requirements with power, adopt same three kinds of different capacities of prescription control and heat-up time, then can make the three kinds of different componentss of ball milling not (or few ball milling) and iron oxide yellow, iron oxide red and the iron black serial target compound of different colours respectively, microwave synthetic product color is much bright-coloured than the conventional high-temperature solid phase method.The present invention adopts homemade LG-MG5520SD type band temperature indicating microwave oven, oscillation frequency 2450MHz, output rating 800W, power input (microwave) 1150W, cavity volume 25L.
The present invention has following three distinguishing features: the one, and adopt a step to urge oxidation and direct microwave method to replace traditional two-step oxidation method; The 2nd, adopt rare earth as oxidation promotor, ultra tiny crystallization agent and nodulizing agent; The 3rd, adopt three sections microwave thermal New Process for Treatment in the building-up process.Adopt industrial residue ferrous sulfate and kaolin, aboundresources, starting material are easy to get, and produce low cost, high-level efficiency, environmental pollution is lacked in the power and energy saving significantly, is an innovative technology of environmental type.Particularly, prepare the advantage that nano level iron-based composite pigment has following four aspects with the inventive method:
1). the present invention has introduced rare earth element and has made functionalized in system, the rare earth of trace can have the oxidation of urgency and micritization and spheroidization effect simultaneously.Than the reaction times that does not add rare earth fast 1/3; The regulation and control grain size promptly adds rare earth ion, obtains the ultra-fine particles of nano-scale and generally present sphere having very strong reflective or target compound that the light transmission features color is bright-coloured or transparent especially, and median size is about 40～100 nanometers.
2). the present invention uses as the rich resource and the ferrous sulfate industrial residue of kaolin, rare earth and so on, can bring into play the national resource advantage, saves cost, again can utilization of waste material, the minimizing environmental pollution.
3). the present invention adopts segmentation microwave radiation synthetic operation Technology, can make the compound new pigment of ultra tiny iron-based of three kinds of different components and three kinds of different colours respectively with same prescription.
4). the present invention compares with prior synthesizing method, and no matter timeliness and effect all can improve 20～30 times, power and energy saving 50～80%, and preparation technology is simple, and easy to operate, the productive rate height is fit to produce in batches.
Fig. 1 is nano combined iron oxide red pigment field emission scanning electron microscope FE-SEM figure.
Fig. 2 is nano combined iron oxide black pigment field emission scanning electron microscope FE-SEM figure.
Can find out among Fig. 1, Fig. 2 that the particle diameter of nano combined pigment is approximately about 100 nanometers.
Embodiment
Embodiment 1: kaolin/Rare Earth Lanthanum/iron oxide based nano combined pigment is synthetic
Earlier with the 20mL pure water kaolin is made into soup compound, takes by weighing after the 5g ferrous sulfate is mixed with it, add less water again and make the ferrous sulfate dissolving and can adsorb and give among the kaolin soup compound, also homodisperse is therein thereupon 0.3g rare earth lanthanum oxalate at this moment.Use 20% microwave power, direct oxidation 25min in air promptly makes iron oxide yellow high-quality pigment; Use high-temperature heat treatment 12min in 80% microwave power then, can make the tiny and uniform iron oxide red high-quality of bright-colored granularity pigment like this; Use 100% microwave power high-temperature heat treatment 11min at last, can make the tiny and uniform high-quality iron oxide black pigment of bright-colored granularity.
Embodiment 2: kaolin/rare earth cerium/iron oxide based nano combined pigment is synthetic
Earlier with the 25mL pure water kaolin is made into soup compound, takes by weighing after the 8g ferrous sulfate is mixed with it, add less water again and make the ferrous sulfate dissolving and can adsorb and give among the kaolin soup compound, also homodisperse is therein thereupon the 0.4g rare earth cerium oxide at this moment.Use 20% microwave power, direct oxidation 28min in air promptly makes iron oxide yellow high-quality pigment; Use high-temperature heat treatment 13min in 80% microwave power then, can make the tiny and uniform iron oxide red high-quality of bright-colored granularity pigment like this; Use 100% microwave power high-temperature heat treatment 9min at last, can make the tiny and uniform high-quality iron oxide black pigment of bright-colored granularity.
Embodiment 3: kaolin/rare earth gadolinium/iron oxide based nano combined pigment is synthetic
Earlier with the 22mL pure water kaolin is made into soup compound, takes by weighing after the 10g ferrous sulfate is mixed with it, add less water again and make the ferrous sulfate dissolving and can adsorb and give among the kaolin soup compound, also homodisperse is therein thereupon 0.5g rare-earth oxidation gadolinium at this moment.Use 20% microwave power, direct oxidation 30min in air promptly makes iron oxide yellow high-quality pigment; Use high-temperature heat treatment 12min in 80% microwave power then, can make the tiny and uniform iron oxide red high-quality of bright-colored granularity pigment like this; Use 100% microwave power high-temperature heat treatment 10min at last, can make the tiny and uniform high-quality iron oxide black pigment of bright-colored granularity.
Embodiment 4: kaolin/rare earth yttrium/iron oxide based nano combined pigment is synthetic
Earlier with the 20mL pure water kaolin is made into soup compound, takes by weighing after the 12g ferrous sulfate is mixed with it, add less water again and make the ferrous sulfate dissolving and can adsorb and give among the kaolin soup compound, also homodisperse is therein thereupon 0.3g rare-earth chlorination yttrium at this moment.Use 40% microwave power, direct oxidation 35min in air promptly makes iron oxide yellow high-quality pigment; Use high-temperature heat treatment 11min in 80% microwave power then, can make the tiny and uniform iron oxide red high-quality of bright-colored granularity pigment like this; Use 100% microwave power high-temperature heat treatment 10min at last, can make the tiny and uniform high-quality iron oxide black pigment of bright-colored granularity.
If do not add kaolin in the raw material, adopt three sections microwave thermal to handle, can synthesize the better rare earth of transparency/iron oxide based nanometer iron oxide yellow, iron oxide red and iron oxide black equally, see following embodiment for details:
Embodiment 5: Rare Earth Lanthanum/iron oxide based nano combined pigment synthetic
Take by weighing 10g FeSO
4.7HO dissolve it with suitable quantity of water, be heated to 40～50 ℃, add 0.01M La (NO
3)
3Solution, under the constant temperature agitation condition, drip 1: 3 ammoniacal liquor rapidly, make divalent iron ion be oxidized to ferric ion, when hierarchy of control pH=6.5, promptly end to add ammoniacal liquor, to form FeO (OH) flocks product this moment, through suction filtration, washing, use 20% microwave power baking 15min then, promptly make transparent yellow iron oxide; Improve microwave power to 60%, high-temperature heat treatment 15min in carrying out promptly makes the transparent iron oxide red composite pigment of ultra micro.Control 80% microwave power, carry out high-temperature heat treatment 18min, promptly make the iron black composite pigment of ultra micro.
Embodiment 6: rare earth cerium/iron oxide based nano combined pigment synthetic
Take by weighing 10g FeSO
4.7HO dissolve it with suitable quantity of water, be heated to 40～50 ℃, add 0.01M CeCl
3Solution, stir at constant temperature, drip 1: 4 ammoniacal liquor rapidly, make divalent iron ion be oxidized to ferric ion, when hierarchy of control pH=7.0, promptly end to add ammoniacal liquor, to form FeO (OH) flocks product this moment, through suction filtration, washing, use 20% microwave power thermal radiation 23min then, promptly make transparent yellow iron oxide; Improve microwave power to 60%, high-temperature heat treatment 10min in carrying out promptly makes the transparent iron oxide red composite pigment of ultra micro.The highest microwave power of control carries out high-temperature heat treatment 12min, promptly makes the iron black composite pigment of ultra micro.
Embodiment 7: rare earth neodymium/iron oxide based nano combined pigment synthetic
Take by weighing 10g FeSO
4.7HO dissolve it with suitable quantity of water, be heated to 40～50 ℃, add 0.01MNd (NO
3)
3Solution, under the constant temperature agitation condition, drip 0.1M NaOH solution rapidly, make divalent iron ion be oxidized to ferric ion, when hierarchy of control pH=7.5, promptly end to add alkali lye, to form FeO (OH) flocks product this moment, through suction filtration, washing, use 40% microwave power baking 15min then, promptly make transparent yellow iron oxide; Improve microwave power to 60%, high-temperature heat treatment 15min in carrying out promptly makes the transparent iron oxide red composite pigment of ultra micro.Control 80% microwave power, carry out high-temperature heat treatment 14min, promptly make the iron black composite pigment of ultra micro.
Embodiment 8: rare earth yttrium/iron oxide based nano combined pigment synthetic
Take by weighing 10g FeSO
4.7HO dissolve it with suitable quantity of water, be heated to 40～50 ℃, add 0.01M Y (NO
3)
3Solution, under the constant temperature agitation condition, drip 0.15M NaOH solution rapidly, make divalent iron ion be oxidized to ferric ion, when hierarchy of control pH=8.0, promptly end to add alkali lye, to form FeO (OH) flocks product this moment, through suction filtration, washing, use 40% microwave power baking 12min then, promptly make transparent yellow iron oxide; Improve microwave power to 60%, high-temperature heat treatment 11min in carrying out promptly makes the transparent iron oxide red composite pigment of ultra micro; Control 80% microwave power, carry out high-temperature heat treatment 12min, promptly make the iron black composite pigment of ultra micro.
Table 1 is the physical property table of kaolin/rare earth/iron oxide based nano combined pigment.
The physical property of table 1 kaolin/rare earth/iron oxide based nano combined pigment
| Sample number | The nanometer iron oxide yellow | The nanometer iron oxide red | The nanometer iron oxide black | |||
| Median size * | Brilliant looks | Median size * | Brilliant looks | Median size * | Brilliant looks | |
| 1 | 100 | Aciculiform | 100 | Spherical | 100 | Spherical |
| 2 | 80 | Aciculiform | 100 | Spherical | 80 | Spherical |
| 3 | 50 | Aciculiform | 80 | The class sphere | 100 | Spherical |
| 4 | 80 | Aciculiform | 40 | Spherical | 40 | Spherical |
| 5 | 100 | Bar-shaped | 100 | Spherical | 100 | Spherical |
| 6 | 80 | Bar-shaped | 80 | Spherical | 80 | Spherical |
| 7 | 100 | Bar-shaped | 50 | Spherical | 50 | Spherical |
| 8 | 40 | Bar-shaped | 80 | Spherical | 100 | Spherical |
* median size adopts field emission scanning electron microscope (FE-SEM) to detect.
Claims (9)
1, a kind of nano oxidized iron-based composite pigment is characterized in that this composite pigment includes rare earth oxide, ferric oxide, and the shared weight percent of each component is:
Rare earth oxide 0.01～1.2%
Ferric oxide 50～98.8%.
2, a kind of nano oxidized iron-based composite pigment as claimed in claim 1 is characterized in that this composite pigment also includes kaolin, and shared weight percent is 0～49%.
3, a kind of method for preparing the nano oxidized iron-based composite pigment of claim 1 or 2, earlier iron vitriol is mixed with rare-earth salts or rare earth oxide before it is characterized in that reacting, or add kaolin simultaneously and be mixed, water is deployed into slurry then, carry out microwave heating treatment again, make the compound new pigment of required nano oxidized iron-based; Feed intake and be by weight: iron vitriol 10～15, rare-earth salts or rare earth oxide 0.01～0.5, kaolin 0～10.
4,, it is characterized in that employed rare-earth salts or rare earth oxide are rare earth oxalate salt or rare earth oxide according to the method for the nano oxidized iron-based composite pigment of the described preparation of claim 3.
5,, it is characterized in that employed kaolin is that chemical constitution is Al according to the method for the nano oxidized iron-based composite pigment of the described preparation of claim 3
2O
32SiO
22H
2O, crystal formation are the kaolin of sheet structure.
6, the method for the nano oxidized iron-based composite pigment of a kind of preparation as claimed in claim 3 is characterized in that microwave heating treatment power is 160～480W, and the time is 15～35min, makes nano iron oxide yellow.
7, the method for the nano oxidized iron-based composite pigment of a kind of preparation as claimed in claim 3 is characterized in that microwave heating treatment power is 320～720W, and the time is 9～18min, makes nanometer iron oxide red.
8, the method for the nano oxidized iron-based composite pigment of a kind of preparation as claimed in claim 3 is characterized in that microwave heating treatment power is 720～800W, and the time is 9～19min, makes nano-sized black iron oxide.
9, the method for the nano oxidized iron-based composite pigment of a kind of preparation as claimed in claim 6, the microwave heating time that it is characterized in that preparing nano iron oxide yellow is 30min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01130133 CN1226354C (en) | 2001-12-28 | 2001-12-28 | Composite gaolinite/rare-earth/iron oxide-base nano pigment and its microwave process for synthesizing it |
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| CN 01130133 CN1226354C (en) | 2001-12-28 | 2001-12-28 | Composite gaolinite/rare-earth/iron oxide-base nano pigment and its microwave process for synthesizing it |
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|---|---|
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| CN1226354C true CN1226354C (en) | 2005-11-09 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322067C (en) * | 2005-06-08 | 2007-06-20 | 刘世琦 | Method for producing iron oxide black |
| CN1297612C (en) * | 2005-06-09 | 2007-01-31 | 上海交通大学 | Method for dispersion of inorganic pigment with high-temperature stability in oily medium |
| CN102181628B (en) * | 2011-03-30 | 2013-02-20 | 攀钢集团有限公司 | Method for producing rich iron ore from ferrous sulfate |
| CN103214879A (en) * | 2013-05-08 | 2013-07-24 | 广东金牌陶瓷有限公司 | Red pigment for ceramic inkjet printing and manufacturing method thereof |
| CN103421356B (en) * | 2013-07-26 | 2015-07-08 | 安徽麒麟化工科技有限公司 | Preparation method of rare earth modified iron oxide black |
| CN104120459B (en) * | 2014-08-06 | 2016-08-17 | 哈尔滨工业大学 | A kind of preparation method of iron-based oxide colored pigment |
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