CN102838170B - Method for preparing transparent iron oxide yellow through wastewater of transparent ferric oxide - Google Patents
Method for preparing transparent iron oxide yellow through wastewater of transparent ferric oxide Download PDFInfo
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- CN102838170B CN102838170B CN201210337322.6A CN201210337322A CN102838170B CN 102838170 B CN102838170 B CN 102838170B CN 201210337322 A CN201210337322 A CN 201210337322A CN 102838170 B CN102838170 B CN 102838170B
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Abstract
The invention discloses a method for preparing transparent iron oxide yellow through wastewater of transparent ferric oxide. The method comprises the following steps: (1) preparing seed crystal: adding a crystal shape control agent to the wastewater of transparent ferric oxide, and slowly adding alkaline solution to adjust the pH (Potential of Hydrogen) to 2 to 5, separating the seed crystal to obtain the reactive liquid with the seed crystal separated; and (2) growing the seed crystal: adding air to the reactive liquid prepared in step (1) under an agitating condition, and slowly adding alkaline solution to adjust the pH to 2 to 7 synchronously, and then carrying out oxidation reaction; and then separating and drying, thus obtaining the transparent iron oxide yellow. According to the method provided by the invention, the wastewater produced by the ferric oxide serves as the raw material for preparing the pigment of transparent iron oxide yellow, therefore, the utilization rate of resource is increased, the pollution to the environment is reduced, and meanwhile, the prepared transparent iron oxide yellow is good in dispersibility, and high in transparency, and can be applied to the wooden ware coating, car repairing paint, plastic, transparent decorative material, cigarette packet and food package industries.
Description
Technical field
The invention belongs to iron oxide pigment field, relate in particular to a kind of preparation method of iron oxide yellow.
Background technology
Transparent yellow iron oxide is a kind of mineral dye being widely used, and characteristic feature is its particle diameter extremely tiny (being generally less than 70nm), diffraction phenomena occurs when irradiate light in the time of surface of pigments and produce transparent effect.Transparent iron oxide pigment not only has the fundamental property of common iron oxide pigment, and pigment has the features such as nontoxic, high transparent, lovely luster, the ultraviolet ray of energy strong absorption.Be widely used in coating, ink, plastics, high having transparent decoration material, tobacco bale and food product pack, light reflecting material and the automobile fields such as paint of showing up.Current synthetic method mainly contains air oxidation process, sodium chlorate oxidation style, carbonyl iron processes etc.
Along with the raising that people require quality of life, transparent ferric oxide is widely used in every field as medium-to-high grade mineral dye, domestic and international market cumulative year after year, and especially domestic Coating Market, between nearly 5 years, consumption increases progressively at double.This is with some decorate properties of current coating industry and require relevant: decorate properties aspect, and high having transparent decoration material, coil coatings for aluminum coil, woodwork coating modelled after an antique, the rise of the industries such as outdoor woodwork coating needs the transparent pigment of a collection of height to match; Coating specification aspect, the pay attention to day by day of country to environmental protection, some have the poisonous tinting material of pollution to be forced forbidding, and this has opened up new market undoubtedly for the transparent ferric oxide of environment-protecting asepsis.
Publication number is that the Chinese patent of CN 1245458C discloses a kind of method that uses refining ferrous sulfate to prepare nano iron oxide yellow, the iron oxide yellow radical length that the method prepares is 100～120nm, but the method needs first ferrous sulfate to be refined.
Publication number is that the Chinese patent of CN 101913656A discloses a kind of method that uses titanium white by product thing ferrous sulfate to prepare iron oxide yellow, under the crystal seed of iron oxide yellow and the existence of urea, control 60～90 DEG C of temperature of reaction, pH value 2.5～4, made iron oxide yellow, but the method needs first ferrous sulfate to be refined.
Transparent ferric oxide is due to the singularity of its technique, and reaction yield generally, between 55-60%, also has a large amount of iron ions to be present among waste water with regard to meaning, especially stoste waste water (abbreviation waste water), and iron concentration is generally 0.1mol/L left and right.Utilize waste water to produce iron oxide yellow and can improve the utilization ratio of resource, and can reduce the pollution of environment, but because iron oxide content in waste water is low and have the interference of sodium sulfate salt, directly utilize waste water to prepare iron oxide yellow also more difficult.
Summary of the invention
The invention provides a kind of method of utilizing transparent ferric oxide waste water to prepare transparent yellow iron oxide, the method takes full advantage of the transparent ferric oxide waste water resource of sulfur acid ferrous iron, has prepared the transparent yellow iron oxide pigments of high transparent, easy dispersion.
Utilize transparent ferric oxide waste water to prepare a method for transparent yellow iron oxide, comprising:
(1) crystal seed preparation: under agitation condition, add chemical additives in transparent ferric oxide waste water, slowly adding basic solution to regulate pH value is 2～5, has crystal seed to separate out, and obtains the reaction solution that crystal seed is separated out;
(2) seeded growth: under agitation condition, pass into air in the reaction solution obtaining to step (1), slowly add wherein basic solution simultaneously, regulation system pH value is 2～7 to carry out oxidizing reaction, after reaction finishes, separate and be dried, obtain described iron oxide yellow;
Described transparent ferric oxide waste water is the waste water producing while producing transparent ferric oxide, and containing after testing iron concentration is 0.05～0.5mol/L;
Described chemical additives is polyphosphoric acid salt, and consumption is 0.2～2% of ferrous ion weight.
In the present invention, in step (1) and step (2), stir speed (S.S.) can be the same or different.
The temperature of reaction of step (1) and (2) is 20-60 DEG C;
It is 0.5-1 hour that step (1) is controlled crystal seed preparation time;
In step (2), the reaction times is 0.5～3 hour.
In above-mentioned preparation method, principal reaction principle is as follows:
FeSO
4+NaOH→Fe(OH)
2+Na
2SO
4
Fe
2(SO
4)
3+NaOH→Fe(OH)
3+Na
2SO
4
Fe(OH)
2+O
2→Fe(OH)
3
Fe(OH)
3→FeOOH+H
2O
In the present invention, polyphosphoric acid salt molecular weight ranges used is 2000-10000, it can be specifically sodium polyphosphate, one or both of potassium polyphosphate, now, described polyphosphoric acid salt not only has stronger sterically hindered effect, also because phosphoric and ferro element have stronger electrocharge effect, can make chemical additives more firmly be combined in pigment particles surface, make pigment particles be difficult for reuniting, finally obtain the pigment particles of the less and narrow distribution of particle diameter.Polyphosphoric acid salt molecular weight is too little, sterically hindered less, is unfavorable for the dispersion of pigment particles, and polyphosphoric acid salt molecular weight is large, is difficult for preparation and poorly water-soluble, the molecular weight of described polyphosphoric acid salt more preferably 4000～7000.
When described polyphosphoric acid salt consumption is too small, do not have the effect of dispersed color particle, usage quantity is excessive, and effect is without considerable change.In the time that the concentration of iron ion in waste water is 0.05～0.1mol/L, the consumption of polyphosphoric acid salt is preferably 1～2% of iron ion weight, most preferably is 1.5～2%.The crystal seed now preparing is best in quality.
Temperature of reaction in step (1) is low, speed of reaction is low, the crystal seed generating is tiny, but easily form stray crystal, temperature is high, and speed of reaction is fast, crystal seed particle diameter is thick, the preparation that is all unfavorable for next step iron oxide yellow too high or too low for temperature, the temperature that the crystal seed in step (1) is separated out is preferably 25-45 DEG C, most preferably is 35 DEG C.
In step (1), pH value is too low, and speed of reaction is slow, and the crystal seed particle diameter making is tiny, and pH value is too high, side reaction easily occurs and produce iron oxide black, and the pH value in step (1) is preferably 2～4.
In the time that the pH value in step (1) is preferably 4～4.5, the temperature of reaction of this step to be carried out preferably, the quality of the crystal seed making is good, is conducive to the preparation of next step iron oxide yellow.
Temperature of reaction in step (2) is low, and speed of reaction is low, and efficiency of pcr product is low, and temperature is high, speed of reaction is fast, and particle diameter is thick, poor transparency, temperature of reaction in step (2) is preferably 25-45 DEG C, most preferably is 30 DEG C, and now crystalline pigment particle diameter is tiny and consistent.
When in step (2), pH value reduces, speed of reaction is low, and efficiency of pcr product is low.When pH value raises, particle size were is large, and transparency is bad, also may produce by product iron oxide black, and the pH value in step (2) is preferably 2-6, and now whole reaction is carried out under weak acid environment, and iron oxide pigment crystalline structure is consistent.
In the time that the pH value in step (2) is preferably 2-6, the temperature of reaction of this step is carried out preferably to the better effects if of the iron oxide yellow making.
In step (2), when stirring, pass into air, when stir speed (S.S.) increases, the iron oxide yellow better quality obtaining, but stir speed (S.S.) increases to certain degree, then it is less on the impact of reaction to increase stir speed (S.S.), energy consumption can increase greatly, stir speed (S.S.) is preferably 100～150r/min, and more preferably 110～130r/min, most preferably is 120r/min;
The air intake of step (2) increases the carrying out that is conducive to oxidizing reaction, but too conference increases energy consumption, and using 1L ferric oxide waste water as reaction solution, in the present invention, the speed that passes into of air is preferably 3～6m3/min, aeration time is preferably 1～2 hour, more preferably 1 hour.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) what this raw material was got is easy, can make resource be reused, and solves again the problem of environmental pollution that may exist from source.
(2) prepared easy dispersion transparent ferric oxide particle diameter is below 70nm, dispersed significantly better than the transparent iron oxide pigment on market, can be widely used in woodwork coating, car refinishing paint, plastics, having transparent decoration material, the industries such as tobacco bale and food product pack, product of the present invention is nonpoisonous and tasteless, reports by SGS.
Brief description of the drawings
Fig. 1 is that the present invention utilizes transparent ferric oxide waste water to prepare the process flow sheet of transparent yellow iron oxide.
Embodiment
Embodiment 1
1, crystal seed preparation:
(1) feed intake: the waste water stoste 1L for preparing transparent ferric oxide generation is joined in reactor, open and stir, detect the ferrous ion concentration of this stoste, ferrous ion concentration is 0.11mol/L.Add sodium polyphosphate (molecular weight is 4000-5000) by 2% of ferrous ion quality, be warming up to 35 DEG C.
(2) add alkali: when stirring, slowly add 30% sodium hydroxide solution, regulate pH value to 4.
2, seeded growth:
With 5m
3the speed of/min passes into air in reactor, and oxidation makes ferrous hydroxide precipitation be converted into ferric hydroxide precipitate, and then changes into alkali formula iron oxide precipitation (being transparent ferric oxide precipitation).30 DEG C of insulation reaction, make crystalline pigment particle diameter tiny and consistent.Slowly add alkali, control pH and be stabilized between 4-4.5, whole reaction is carried out under weak acid environment, ensure that crystalline pigment structure is consistent.Continue oxidation one hour, reaction finishes to filter, and rinsing, dry, pulverize, and obtains transparent iron oxide yellow, productive rate 71%.
Embodiment 2
Utilize the preparation of transparent ferric oxide waste water easily to disperse the preparation method of transparent yellow iron oxide, its step is identical with embodiment 1, and difference is: while adding alkali, control temperature at 25 DEG C.
Embodiment 3
Utilize the preparation of transparent ferric oxide waste water easily to disperse the preparation method of transparent yellow iron oxide, its step is identical with embodiment 1, and difference is: while adding alkali, control temperature at 45 DEG C.
Embodiment 4
Utilize the preparation of transparent ferric oxide waste water easily to disperse the preparation method of transparent yellow iron oxide, its step is identical with embodiment 1, and difference is: while adding alkali, control temperature at 55 DEG C.
Embodiment 5
Utilize the preparation of transparent ferric oxide waste water easily to disperse the preparation method of transparent yellow iron oxide, its step is identical with embodiment 1, and difference is: when insulation reaction, control pH 3.5.
Embodiment 6
Utilize the preparation of transparent ferric oxide waste water easily to disperse the preparation method of transparent yellow iron oxide, its step is identical with embodiment 1, and difference is: when insulation reaction, control pH 5.5.
Embodiment 7
Utilize the preparation of transparent ferric oxide waste water easily to disperse the preparation method of transparent yellow iron oxide, its step is identical with embodiment 1, and difference is: when insulation reaction, control pH 6.5.
Embodiment 8
Utilize the preparation of transparent ferric oxide waste water easily to disperse the preparation method of transparent yellow iron oxide, its step is identical with embodiment 1, and difference is: selected sodium polyphosphate molecular weight is 2000-3000.
Embodiment 9
Utilize the preparation of transparent ferric oxide waste water easily to disperse the preparation method of transparent yellow iron oxide, its step is identical with embodiment 1, and difference is: selected sodium polyphosphate molecular weight is 3000-4000.
Embodiment 10
Utilize the preparation of transparent ferric oxide waste water easily to disperse the preparation method of transparent yellow iron oxide, its step is identical with embodiment 1, and difference is: selected sodium polyphosphate molecular weight is 5000-6000.
The product index analytical data of table 1 embodiment 1,2,3 and 4
The product index analytical data of table 2 embodiment 1,5,6 and 7
The product index analytical data of table 3 embodiment 1,8,9 and 10
Rank term glossiness, transparency, viscosity, coloured light, look force inspecting conclusion etc.
The approximate larger 6--of the obvious 5---of the medium 4---of the small 3---of the trickle 2--of 1--of 0--is very large
Color term
The transparent OP---of the green Y---of the red G---of the R---poor T-of the good W---of the gorgeous E---of the blue dark P---of the bright D---of L---of yellow B---is opaque
While adding alkali as can be seen from Table 1 and Table 2, excess Temperature and too low iron oxide yellow dispersiveness and the tinting strength preparing all decline, and when insulation reaction, along with the rising of pH value, tinting strength increases, but transparency reduces greatly.
Product index detection method:
The pigment that the present invention is obtained carries out product index detection after being prepared into mill base, and the weight percent of described mill base is composed as follows:
Bisphenol A-type vinyl ester resin V-411:40%
Petroleum solvent: 8%
Dispersion agent: 12%
Pigment: 40%
1, dispersed detection: standard and test sample to be checked are filled a prescription after mixing by above, disperse 1 hour in mixing machine, sampling detects standard specimen and treats test sample mill base fineness with Hai Geman grindometer, draws pigment-dispersing.
2, the detection of transparency and tinting strength: above mixture disperses in the rotary and vibrating mixer of skankex450, and colo(u)rant dispersion, to being less than 5um, is made to mill base.Then
(1) in varnish, add 50% mill base, make 30um colour atla, contrast with standard specimen, estimate to obtain form and aspect, computer color measurement instrument is measured pigment transparency.
(2) in white alkyd paint, add 2.5% mill base to make 120um colour atla, contrast with standard specimen, computer color measurement instrument is measured pigmenting power.
Claims (7)
1. utilize transparent ferric oxide waste water to prepare a method for transparent yellow iron oxide, it is characterized in that, comprising:
(1) crystal seed preparation: under agitation condition, add chemical additives in transparent ferric oxide waste water, slowly adding basic solution to regulate pH value is 2～5, has crystal seed to separate out, and obtains the reaction solution that crystal seed is separated out;
The temperature that crystal seed is separated out is 25～45 DEG C;
(2) seeded growth: under agitation condition, pass into air in the reaction solution obtaining to step (1), slowly add wherein basic solution simultaneously, regulation system pH value is 2～7 to carry out oxidizing reaction, after reaction finishes, separate and be dried, obtain described transparent yellow iron oxide;
In described transparent ferric oxide waste water, the concentration of ferrous ion is 0.05～0.5mol/L;
Described chemical additives is polyphosphoric acid salt, and consumption is 0.2～2% of ferrous ion weight;
The molecular weight of described polyphosphoric acid salt is 4000～7000;
Temperature of reaction in step (2) is 25～45 DEG C.
2. the method for utilizing transparent ferric oxide waste water to prepare transparent yellow iron oxide according to claim 1, is characterized in that, when the concentration of described ferrous ion is 0.05～0.1mol/L, the consumption of described polyphosphoric acid salt is 1～2% of iron ion weight.
3. the method for utilizing transparent ferric oxide waste water to prepare transparent yellow iron oxide according to claim 1, is characterized in that, in step (1), pH value is 2～4.
4. the method for utilizing transparent ferric oxide waste water to prepare transparent yellow iron oxide according to claim 1, is characterized in that, in step (2), pH value is 2-6.
5. the method for utilizing transparent ferric oxide waste water to prepare transparent yellow iron oxide according to claim 1, is characterized in that, the stir speed (S.S.) in step (2) is 100～150r/min.
6. the method for utilizing transparent ferric oxide waste water to prepare transparent yellow iron oxide according to claim 5, is characterized in that, described stir speed (S.S.) is 110～130r/min.
7. the method for utilizing transparent ferric oxide waste water to prepare transparent yellow iron oxide according to claim 1, is characterized in that, in the time that the volume of transparent ferric oxide waste water is 1L, the speed that in step (2), air passes into is 3～6m
3/ min, the time of passing into is 1～2 hour.
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| CN102838170B true CN102838170B (en) | 2014-09-24 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4459276A (en) * | 1981-09-17 | 1984-07-10 | Agency Of Industrial Science & Technology | Yellow iron oxide pigment and method for manufacture thereof |
| CN1415666A (en) * | 2002-12-04 | 2003-05-07 | 中国化工建设总公司常州涂料化工研究院 | Method for producing the yellow pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white |
| CN101423257A (en) * | 2008-11-07 | 2009-05-06 | 浙江正奇化工有限公司 | Preparation method of nanoscale iron oxide red |
| CN101746835A (en) * | 2009-12-25 | 2010-06-23 | 浙江工业大学 | Method for preparing iron oxide yellow pigment by carrying out resourceful treatment on pyrite wastewater |
-
2012
- 2012-09-13 CN CN201210337322.6A patent/CN102838170B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4459276A (en) * | 1981-09-17 | 1984-07-10 | Agency Of Industrial Science & Technology | Yellow iron oxide pigment and method for manufacture thereof |
| CN1415666A (en) * | 2002-12-04 | 2003-05-07 | 中国化工建设总公司常州涂料化工研究院 | Method for producing the yellow pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white |
| CN101423257A (en) * | 2008-11-07 | 2009-05-06 | 浙江正奇化工有限公司 | Preparation method of nanoscale iron oxide red |
| CN101746835A (en) * | 2009-12-25 | 2010-06-23 | 浙江工业大学 | Method for preparing iron oxide yellow pigment by carrying out resourceful treatment on pyrite wastewater |
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Address after: 312366, Youyi Town, Zhejiang City, Shangyu province Shaoxing friendship gate Patentee after: Zhejiang miracle Technology Co., Ltd. Address before: 312366, Youyi Town, Zhejiang City, Shangyu province Shaoxing friendship gate Patentee before: Zhejiang Genky Chemical Co., Ltd. |