CN102126759B - Environment-friendly synthesis method of pigment-grade iron oxide red - Google Patents
Environment-friendly synthesis method of pigment-grade iron oxide red Download PDFInfo
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- CN102126759B CN102126759B CN 201110021205 CN201110021205A CN102126759B CN 102126759 B CN102126759 B CN 102126759B CN 201110021205 CN201110021205 CN 201110021205 CN 201110021205 A CN201110021205 A CN 201110021205A CN 102126759 B CN102126759 B CN 102126759B
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Abstract
The invention discloses an environment-friendly synthesis method of pigment-grade iron oxide red. The method comprises the following steps: by taking ferric salt or ferrous salt as a raw material, respectively regulating the pH to 7 and 9 so as to respectively prepare amorphous hydrated ferric oxide seed crystal and delta-FeOOH seed crystal; respectively adding the seed crystals in a reaction kettle, so that the concentrations of the seed crystals are 0.0125mol/L and 0.07mol/L respectively; respectively controlling the temperature to 90-95 DEG C and 90-100 DEG C; adding a Fe<2+> ion catalyst (a ferrous chloride solution or a ferrous sulfate solution) to react for 0.5 hour; adding 30g of excess waste scrap iron, introducing air, supplementing a ferrite solution in a reaction process, maintaining the concentration of ferrous ion in the reaction system to 0.16-0.20 mol/L, and reacting for 48-82 hours; and filtering, washing and drying the product so as to obtain the pigment-grade iron oxide red powder with a good pigment property. The environment-friendly synthesis method has no environment pollution and low raw material cost, and process condition is easy to control, thus an effective, practicable and environment-friendly novel method is provided for the industrial production of the pigment-grade iron oxide red.
Description
Technical field
The present invention relates to a kind of green synthesis method of pigment-level red iron oxide, belong to the mineral dye preparing technical field.
Background technology
Red iron oxide is Industrial products as a kind of conventional oxidation iron, in China about 50 years developing history has been arranged.Because it has higher chemistry and physical stability; And good performances such as the variety of color, high covering power and nontoxicity; Be widely used in the tinting material of rubber, paint, artificial marble, and in the industries such as pottery, papermaking, printing ink and art painting.The pigment-level red iron oxide product that China produces accounts for the 60%-70% of Gross World Product, wherein 50% outlet.Therefore, the ferric oxide red colorant production technique is constantly studied and improved, more help promoting healthy, stable, the development enduringly of China's ferric oxide red colorant industry.In the prior art; The preparation method of ferric oxide red colorant is divided into dry method and wet method (The IronOxides; Wiley-VCH, Weinheim 2003,525-531); The quality that wherein adopts wet method to obtain the red iron oxide product will obviously be better than dried preparation, so the general wet method that adopts prepares ferric oxide red colorant on the industrial production.Its reaction process is following: at first prepare iron red crystal seed formation, then this crystal seed is placed reaction kettle, add iron filings, water and a certain amount of divalent iron salt, 90 ℃ of following blowing air oxidations, when the product color reached needed standard, reaction finished.Different preparing methods and the kind of adding divalent iron salt according to iron red crystal seed formation; Wet method prepares the red iron oxide technology and is divided into nitrate method, sulfuric acid process and mixed acid process: (1) nitrate method: the preparation of iron red crystal seed formation adopts iron filings, water and certain density nitric acid under 85 ℃ temperature, to react acquisition; Add Iron nitrate (inorganic chemicals industry in the second oxidation process; 1997,6,5-6); (2) sulfuric acid process: FeSO is adopted in the preparation of iron red crystal seed formation
4Solution is that the bubbling air oxidation obtains under the 9-11 in the pH value, add in the second oxidation process ferrous sulfate (inorganic chemicals industry, 2006,38 (4), 49-50); (3) mixed acid process: the crystal seed that the preparation of iron red crystal seed formation adopts nitrate method to obtain, add in the second oxidation process ferrous sulfate (AIChE, 2008,27 (2), 263-268).The resulting red iron oxide product of above-mentioned three kinds of preparing methods is the best with the pigment performance of nitrate method products obtained therefrom.But in the process that adopts nitrate method, not only can produce a large amount of NO
xGas, and in the second oxidation process, also can produce a large amount of ammonia nitrogen waste liquids, as not handling, directly discharging certainly will cause the pollution of sky G&W.Waste gas, the waste water that nitrate method is produced carry out environmental protection treatment (AIChE, 2008,27 (2), 263-268), can increase the production cost of enterprise to a great extent.For fear of these problems, and some enterprises' employing sulfuric acid processs and mixed acid process production technique (inorganic chemicals industry, 2006,38 (4), 49-50).Wherein, though that sulfuric acid process is polluted is little, cost is low, and the quality product that obtains can not show a candle to nitrate method, and product color is dim, and pigment performance is relatively poor relatively.The ferric oxide red colorant capability and performance that mixed acid process obtains is better relatively, but needs to adopt the nitric acid crystal seed, can cause NO to a certain degree
xGas contamination.More than these unfavorable factors hindered the normal development of many ferric oxide red colorants manufacturing enterprise greatly.For this reason, research obtains the good and free of contamination again ferric oxide red colorant working method with low cost of color characteristics, and is significant.
Summary of the invention
The green synthesis method that the purpose of this invention is to provide a kind of pigment-level red iron oxide has solved prior art nitrate method and mixed acid process and has produced the NO that produces in the ferric oxide red colorant process
xThe problem that gas and ammonia nitrogen waste liquid pollute environment.
The technical scheme that the present invention takes is such.A kind of green synthesis method one of pigment-level red iron oxide may further comprise the steps:
(1) with the ferric salt solution be raw material, adding sodium hydroxide solution adjusting pH is 7, at room temperature makes unsetting hydrous iron oxide crystal seed;
(2) the unsetting hydrous iron oxide crystal seed that step (1) is made joins in the reaction kettle, 90～95 ℃ of controlled temperature, and making seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding Fe
2+Ionic catalyst, reaction 0.5h adds 30g scrap iron skin again; Bubbling air; Adding by-product ferrous sulfate during or the iron and steel pickling waste liquid of producing white titanium pigment in the reaction process, is 0.16～0.20mol/L with the concentration of keeping the reaction system ferrous ion, reaction 48～72h; Product is through filtering, wash, drying, and it is iron oxide red to obtain pigment-level.
The present invention can also take following technical scheme: a kind of green synthesis method two of pigment-level red iron oxide may further comprise the steps:
(1) with the copperas solution be raw material, adding sodium hydroxide solution adjusting pH is 9, at room temperature adds ydrogen peroxide 50, makes unsetting δ-FeOOH crystal seed;
Unsetting δ-FeOOH the crystal seed that (2) will make joins in the reaction kettle, 90～100 ℃ of controlled temperature, and making seed concentration is 0.07mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.03: 1 adding Fe
2+Behind the ionic catalyst, reaction 0.5h adds 30g scrap iron skin again; Bubbling air; Adding the by-product ferrous sulfate during of producing white titanium pigment or the iron and steel pickling waste liquid that contains ferrous ion in the reaction process, is 0.16～0.20mol/L with the concentration of keeping the reaction system ferrous ion, reaction 48-72h; Product is through filtering, wash, drying, and it is iron oxide red to obtain pigment-level.
Among the present invention, the crystal seed of preparation pigment-level red iron oxide is respectively hydrous iron oxide crystal seed or δ-FeOOH crystal seed.
In method one of the present invention, said trivalent iron salt is iron nitrate (Fe (NO
3)
3), iron(ic)chloride (FeCl
3), ferric sulfate (Fe
2(SO
4)
3) wherein a kind of.
Among the present invention, said Fe
2+Ionic catalyst is iron protochloride (FeCl
2) solution or ferrous sulfate (FeSO
4) a kind of in the solution.
The prepared iron oxide red pattern of pigment-level of the present invention is that the good standard of crystallization is cube shaped and accurate octahedra, and pigment performance is good.
The beneficial effect that the present invention obtains is: the present invention is a crystal seed with hydrous iron oxide or δ-FeOOH; By-product ferrous sulfate during or iron and steel pickling waste liquid with waste iron filing and production white titanium pigment are raw material; Prepare and have the iron oxide red of good pigment performance; The discharging of preparation technology's non-environmental-pollution thing, with low cost, economical and practical.Not only reduced production cost, also realized producing the utilization of waste liquid and mechanical workout waste material.
Description of drawings
Fig. 1 is the stereoscan photograph of embodiment 9 prepared products.
Fig. 2 is the stereoscan photograph of embodiment 10 prepared products.
Fig. 3 is the stereoscan photograph of embodiment 11 prepared products.
Embodiment
Following examples are used to explain the present invention.
Embodiment 1
Concentration is the Fe (NO of 2mol/L
3)
3Solution 50ml under agitation, regulates pH=7 with 6.0mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, can make unsetting hydrous iron oxide crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g; Bubbling air is added the waste liquid of producing white titanium pigment in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 90 ℃, reaction 48h, and product filters; Washed several times with water can get the about 23g of product after the drying.
Embodiment 2
Concentration is the Fe (NO of 2mol/L
3)
3Solution 50ml under agitation, regulates pH=7 with 6.0mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, can make unsetting hydrous iron oxide crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding ferrous sulfate (FeSO
4) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 90 ℃, reaction 48h, and product filters; Washed several times with water can get the about 23g of product after the drying.
Embodiment 3
Concentration is the Fe (NO of 2mol/L
3)
3Solution 50ml under agitation, regulates pH=7 with 6.0mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, can make unsetting hydrous iron oxide crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.20mol/L; Temperature of reaction system maintains 90 ℃, reaction 48h, and product filters; Washed several times with water can get the about 20g of product after the drying.
Embodiment 4
Concentration is the Fe (NO of 2mol/L
3)
3Solution 50ml under agitation, regulates pH=7 with 6.0mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, can make unsetting hydrous iron oxide crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 90 ℃, reaction 72h, and product filters; Washed several times with water can get the about 24g of product after the drying.
Embodiment 5
Concentration is the Fe (NO of 2mol/L
3)
3Solution 50ml under agitation, regulates pH=7 with 6.0mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, can make unsetting hydrous iron oxide crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.20mol/L; Temperature of reaction system maintains 90 ℃, reaction 72h, and product filters; Washed several times with water can get the about 22g of product after the drying.
Embodiment 6
Concentration is the Fe (NO of 2mol/L
3)
3Solution 50ml under agitation, regulates pH=7 with 6.0mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, can make unsetting hydrous iron oxide crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 95 ℃, reaction 48h, and product filters; Washed several times with water can get the about 20g of product after the drying.
Embodiment 7
Concentration is the FeCl of 2mol/L
3Solution 50ml under agitation, regulates pH=7 with 6.0mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, can make unsetting hydrous iron oxide crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 90 ℃, reaction 48h, and product filters; Washed several times with water can get the about 19g of product after the drying.
Embodiment 8
Concentration is the FeCl of 2mol/L
3Solution 50ml under agitation, regulates pH=7 with 6.0mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, can make unsetting hydrous iron oxide crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g; Bubbling air is added ferrous salt (spent pickle liquor that contains ferrous ion) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 90 ℃, reaction 48h, and product filters; Washed several times with water can get the about 17g of product after the drying.
Embodiment 9
Concentration is the Fe of 1mol/L
2(SO
4)
3Solution 50ml under agitation, regulates pH=7 with 6.0mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, can make unsetting hydrous iron oxide crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 90 ℃, reaction 48h, and product filters; Washed several times with water can get the about 17g of product after the drying, the stereoscan photograph of product is seen accompanying drawing 1.
Embodiment 10
Concentration is the FeSO of 1.2mol/L
4Solution 50ml under agitation, regulates pH=9 with 6mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, and it is 30% H that room temperature adds massfraction next time
2O
23.1ml, behind the stirring 30min, can make unsetting δ-FeOOH crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.07mol/L, adds Fe again
2+Ionic catalyst is according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.03: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g again; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 100 ℃, reaction 48h, and product filters; Washed several times with water can get the about 29g of product after the drying, the stereoscan photograph of product is seen accompanying drawing 2.
Embodiment 11
Concentration is the FeSO of 1.2mol/L
4Solution 50ml under agitation, regulates pH=9 with 6mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, and it is 30% H that room temperature adds massfraction next time
2O
23.1ml, behind the stirring 30min, can make unsetting δ-FeOOH crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.07mol/L, adds Fe again
2+Ionic catalyst is according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.03: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g again; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 100 ℃, reaction 72h, and product filters; Washed several times with water can get the about 40g of product after the drying, the stereoscan photograph of product is seen accompanying drawing 3.
Embodiment 12
Concentration is the FeSO of 1.2mol/L
4Solution 50ml under agitation, regulates pH=9 with 6mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, and it is 30% H that room temperature adds massfraction next time
2O
23.1ml, behind the stirring 30min, can make unsetting δ-FeOOH crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.07mol/L, adds Fe again
2+Ionic catalyst is according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.03: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g again; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 90 ℃, reaction 48h, and product filters; Washed several times with water can get the about 27g of product after the drying.
Embodiment 13
Concentration is the FeSO of 1.2mol/L
4Solution 50ml under agitation, regulates pH=9 with 6mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, and it is 30% H that room temperature adds massfraction next time
2O
23.1ml, behind the stirring 30min, can make unsetting δ-FeOOH crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.07mol/L, adds Fe again
2+Ionic catalyst is according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.03: 1 adding ferrous sulfate (FeSO
4) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g again; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 100 ℃, reaction 48h, and product filters; Washed several times with water can get the about 29g of product after the drying.
Embodiment 14
Concentration is the FeSO of 1.2mol/L
4Solution 50ml under agitation, regulates pH=9 with 6mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, and room temperature adds quality next time, and to divide 7 numbers be 30% H
2O
23.1ml, behind the stirring 30min, can make unsetting δ-FeOOH crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.07mol/L, adds Fe again
2+Ionic catalyst is according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.03: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g again; Bubbling air is added ferrous salt (producing the waste liquid of white titanium pigment) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.20mol/L; Temperature of reaction system maintains 100 ℃, reaction 48h, and product filters; Washed several times with water can get the about 25g of product after the drying.
Embodiment 15
Concentration is the FeSO of 1.2mol/L
4Solution 50ml under agitation, regulates pH=9 with 6mol/L NaOH solution, and the volume constant volume with the suspension that generates is 200ml simultaneously, and it is 30% H that room temperature adds massfraction next time
2O
23.1ml, behind the stirring 30min, can make unsetting δ-FeOOH crystal seed; Crystal seed is transferred in the reaction kettle, and seed concentration is 0.07mol/L, adds Fe again
2+Ionic catalyst is according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.03: 1 adding iron protochloride (FeCl
2) behind the catalyzer, reaction 0.5h adds the excessive scrap iron skin of 30g again; Bubbling air is added ferrous salt (spent pickle liquor that contains ferrous ion) in the reaction process, the concentration of keeping the reaction system ferrous ion is 0.16mol/L; Temperature of reaction system maintains 100 ℃, reaction 48h, and product filters; Washed several times with water can get the about 21g of product after the drying.
Claims (4)
1. the green synthesis method of a pigment-level red iron oxide is characterized in that may further comprise the steps:
(1) with the ferric salt solution be raw material, adding sodium hydroxide solution adjusting pH is 7, at room temperature makes unsetting hydrous iron oxide crystal seed;
(2) the unsetting hydrous iron oxide crystal seed that step (1) is made joins in the reaction kettle, 90～95 ℃ of controlled temperature, and making seed concentration is 0.125mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.05: 1 adding Fe
2+Behind the ionic catalyst, reaction 0.5h adds the excessive scrap iron skin of 30g again; Bubbling air; Adding by-product ferrous sulfate during or the iron and steel pickling waste liquid of producing white titanium pigment in the reaction process, is 0.16～0.20mol/L with the concentration of keeping the reaction system ferrous ion, reaction 48～72h; Product is through filtering, wash, drying, and it is iron oxide red to obtain pigment-level.
2. the green synthesis method of pigment-level red iron oxide according to claim 1 is characterized in that: trivalent iron salt is wherein a kind of of iron nitrate, iron(ic)chloride, ferric sulfate.
3. the green synthesis method of a pigment-level red iron oxide is characterized in that may further comprise the steps:
(1) with the copperas solution be raw material, adding sodium hydroxide solution adjusting pH is 9, at room temperature adds ydrogen peroxide 50, makes unsetting δ-FeOOH crystal seed;
Unsetting δ-FeOOH the crystal seed that (2) will make joins in the reaction kettle, and controlled temperature 90-100 ℃, making seed concentration is 0.07mol/L, according to the Fe that adds
2+The contained Fe of crystal seed in mole number and the reaction system of ion in reaction system
3+The ratio of ionic mole number is 0.03: 1 adding Fe
2+Behind the ionic catalyst, reaction 0.5h adds the excessive scrap iron skin of 30g again; Bubbling air; Adding the by-product ferrous sulfate during of producing white titanium pigment or the iron and steel pickling waste liquid that contains ferrous ion in the reaction process, is 0.16～0.20mol/L with the concentration of keeping the reaction system ferrous ion, reaction 48～72h; Product is through filtering, wash, drying, and it is iron oxide red to obtain pigment-level.
4. according to the green synthesis method of claim 1 or 2 or 3 described pigment-level red iron oxides, it is characterized in that Fe
2+Ionic catalyst is that solution of ferrous chloride or copperas solution are wherein a kind of.
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| CN106219611B (en) * | 2016-07-27 | 2017-07-11 | 升华集团德清华源颜料有限公司 | A kind of low viscosity iron oxide yellow |
| CN106430326B (en) * | 2016-10-17 | 2018-02-06 | 中国有色集团（广西）平桂飞碟股份有限公司 | The method of the ultra-fine seed production high-performance iron oxide red of hydro-thermal |
| CN109896550B (en) * | 2019-04-29 | 2021-06-22 | 中钢集团南京新材料研究院有限公司 | Method for preparing iron oxide red by recycling ternary precursor waste liquid |
| CN112875762B (en) * | 2021-01-30 | 2022-05-17 | 河北粤海水务集团有限公司 | Method for preparing iron oxide red by using iron-containing pickling waste liquid |
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| CN86100780A (en) * | 1986-01-28 | 1987-10-07 | 淄博钴厂 | A kind of manufacture method of ferric oxide red colorant |
| CN1077206A (en) * | 1992-04-08 | 1993-10-13 | 李文政 | Method for preparing iron oxide red from iron mud waste residue |
| US20080098912A1 (en) * | 2006-10-30 | 2008-05-01 | Sang Broli Company Limited | Process and compound for producing printed design creating three-dimensional visual effect |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100780A (en) * | 1986-01-28 | 1987-10-07 | 淄博钴厂 | A kind of manufacture method of ferric oxide red colorant |
| CN1077206A (en) * | 1992-04-08 | 1993-10-13 | 李文政 | Method for preparing iron oxide red from iron mud waste residue |
| US20080098912A1 (en) * | 2006-10-30 | 2008-05-01 | Sang Broli Company Limited | Process and compound for producing printed design creating three-dimensional visual effect |
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