CN102390870B - Preparation method of superfine iron oxide red pigment with high glossiness and pure red tone - Google Patents
Preparation method of superfine iron oxide red pigment with high glossiness and pure red tone Download PDFInfo
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- CN102390870B CN102390870B CN 201110233356 CN201110233356A CN102390870B CN 102390870 B CN102390870 B CN 102390870B CN 201110233356 CN201110233356 CN 201110233356 CN 201110233356 A CN201110233356 A CN 201110233356A CN 102390870 B CN102390870 B CN 102390870B
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- iron oxide
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- crystal seed
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Abstract
The invention mainly discloses a preparation method of a superfine iron oxide red pigment with high glossiness and pure red tone. The preparation method comprises the following steps of: preparing a solution from refined ferrous sulfate, neutralizing the solution with a mixed alkaline solution, heating to 40-50 DEG C, and oxidizing to obtain special seed crystals; carrying out secondary oxidization under the condition of existence of seed crystals, depositing generated iron sesquioxide on special crystal nucleus, neutralizing diluted ammonia water with the concentration of about 8 percent by using the generated sulfuric acid, controlling PH of the system to 3.0-5.0, continuously dropwise adding the ferrous sulfate and the diluted ammonia water, and gradually growing the crystal nucleus to form the orange red iron oxide pigment; and pulping an organic red iron oxide filter cake, and calcining at high temperature to obtain the superfine iron oxide red pigment with high glossiness and pure red tone. The preparation method disclosed by the invention has the advantages that: the superfine iron oxide red pigment with high glossiness and pure red tone is prepared by utilizing the preparation method disclosed by the invention; and the preparation method is realized by using a method of reducing the influence degree to the environment and has favorable environment-friendly effect.
Description
Technical field
The present invention relates to the preparation method of the pure red accent superfine iron oxide of a kind of high gloss red, specifically is that a kind of employing titanium white by product ferrous sulfate is raw material, prepares crystal seed earlier, and the oxidation ferrous sulfate makes this product in the presence of this crystal seed.
Background technology
Ferric oxide red colorant is because it is nontoxic, abundant raw material, and superior performance, cheap and be widely used in coating, products such as building materials and rubber and plastic painted.Water-borne coatings is widely-used in recent years, and common ferric oxide red colorant can not satisfy its high gloss, the requirement of high color purity.Tracing it to its cause is the limitation that is subjected to the preparation method.The following method of the general employing of the preparation of red iron oxide at present:
1. nitration mixture salt method: after preparing crystal seed with nitric acid and iron sheet, in the presence of Iron nitrate, carry out second oxidation in advance, add ferrous sulfate at last and carry out oxidation.The gloss of its pigment is influenced by Iron nitrate and ferrous sulfate usage ratio, and the purity of color of pigment is very responsive to the post-treating method of pigment, and behind the pigment grind, the red degree of its true qualities can descend.Ammonia nitrogen in the factory effluent will be removed by complicated technology.
2. sulphate process: after preparing crystal seed with ferrous sulfate and alkali, in the presence of ferrous sulfate, carry out second oxidation.The crystal seed preparation feedback is difficult to grasp, the pigment quality instability that obtains, and tinctorial strength is low, and red degree is low.
3. iron oxide black calcination method: calcine general iron oxide black, can only obtain dark ferric oxide red colorant.
4. iron oxide yellow calcination method: can obtain versicolor ferric oxide red colorant by the control of calcining temperature, but because oil number is too high, be difficult to obtain the red iron oxide of the pure red accent of high gloss.
5. ferrous sulfate calcination method: can obtain the high ferric oxide red colorant of purity of color, but produce a large amount of sulfide waste gas in producing, need huge emission-control equipment.
Summary of the invention
The present invention aims to provide the preparation method of the pure red accent superfine iron oxide of a kind of high gloss red, specifically is a kind of gloss and red degree height, and the preparation method of the pure red accent superfine iron oxide of environment amenable high gloss red.
In order to solve above technical problem, the preparation method of the pure red accent superfine iron oxide of a kind of high gloss of the present invention red, being mainly and adopting ferrous sulfate is that raw material is made crystal seed, second oxidation gets ferric oxide under the condition that this crystal seed exists, again to ferric oxide filter, wash, calcine, grind ferric oxide red colorant; It is characterized in that: being made as of described crystal seed: it is 40 ~ 100 g/L solution that refining ferrous sulfate is mixed with concentration, uses a certain proportion of NaOH and Mg (OH) then
2Mix in the alkaline solution and above-mentioned solution to pH=9.0 ~ 10.0, the bubbling air oxidation makes crystal seed under 40 ~ 50 ℃ of temperature; Reaction equation is:
FeSO
4+2NaOH=Fe(OH)
?2↓+Na
2SO
4
FeSO
4+?Mg(OH)
?2=Fe(OH)
?2↓+?Mg?SO
4
2Fe(OH)
2+1/2O
2=2γ-FeOOH+H
2O
Crystal seed transforms: 2 γ-FeOOH → α-Fe
2O
3XH
2O (crystal seed)+H
2O;
Described second oxidation technology is:
Above-mentioned crystal seed is added water latting drown to 1 ~ 1.5 times, adding ferrous sulfate solution to ferrous content is 30 ~ 70g/L, bubbling air carried out oxidation after intensification reached 80 ~ 85 ℃, the ferric oxide that generates is deposited on the above-mentioned nucleus, the sulfuric acid of Sheng Chenging neutralizes with 8% weak ammonia simultaneously, hierarchy of control pH=3.0 ~ 5.0 drip ferrous sulfate and weak ammonia continuously, and nucleus is grown up gradually and formed orange red iron oxide pigment; The second oxidation reaction formula is as follows:
2FeSO
4+1/2O
2+2H
2O=Fe
2O
3?·?xH
2O↓+2H
2SO
4?
H
2SO
4+2NH
3?·?H
2O?=(NH
4)
2SO
4?+2H
2O；
Described calcining process is:
With above-mentioned after filtration, the orange red ferric oxide filter cake making beating that obtains after up to standard of washing, and calcine, control high-temperature zone temperature is 800 ℃, calcination time is 60 minutes, calcination product is after the air at room temperature cooling, and superfine grinding finally obtains the pure red accent superfine iron oxide of high gloss red.The calcination reaction equation is:
Further, described crystal seed preparation mixes Mg (OH) in the alkaline solution
2With the 30%NaOH mass ratio be 1:20 ~ 1:5.
In order to understand the present invention better, below be the concrete preparation technology of the pure red accent superfine iron oxide of high gloss of the present invention red:
With ferrous 40 ~ 100 g/L solution that are mixed with of POV, use Mg (OH) then
2With the 30%NaOH mass ratio be 1:20 ~ 1:5 mix in the alkaline solution and above-mentioned solution to pH=9.0 ~ 10.0, Heating temperature to 40 ~ 50 ℃, feeding flow again is 14 ~ 18M
3The air of/min carries out oxidation, makes special crystal seed.Then above-mentioned crystal seed is added water latting drown to 1 ~ 1.5 times, adding ferrous sulfate solution to ferrous content is 30 ~ 70g/L, and heating up and feeding flow after reaching 80 ~ 85 ℃ is 14 ~ 18M
3/ min air carries out oxidation, the ferric oxide that generates is deposited on the special nucleus, and the sulfuric acid of Sheng Chenging neutralizes hierarchy of control pH=3.0 ~ 5.0 with 8% left and right sides weak ammonia simultaneously, drip ferrous sulfate and weak ammonia continuously, nucleus is grown up gradually and is formed orange red iron oxide pigment.With above-mentioned after filtration, the orange red ferric oxide filter cake making beating that obtains after up to standard of washing, and to pump into diameter be 1.5 meters, length is to calcine in 24 meters the rotary kiln, control high-temperature zone temperature is 800 ℃, is 60 minutes at kiln residence time.Calcination product is carried out superfine grinding with Cyclone mill after the air at room temperature cooling, finally obtain the pure red accent superfine iron oxide of high gloss red.
Special crystal seed by the preparation of this Technology, pass through series reaction, the ferric oxide red colorant granulin molecule that finally obtains is shaped as diamond shaped, clear-cut all around, there is not any branch, particle integrity, high conformity, original median size 0.25 ~ 0.35 μ m, and after removing crystal water by high-temperature calcination, Fe
2O
3Content is more than 99.5%, the chemical purity height, at last by the Cyclone mill superfine grinding, make finally to obtain ferric oxide red colorant and have high gloss, high color purity, red color tone distinctness pure, ultra-fine (Hegman fineness 〉=6 grade, corresponding film thickness≤25 μ m), easy characteristic such as dispersion.
The invention has the advantages that: the present invention adopts the titanium white by product ferrous sulfate, and adulterated alkaline-earth metal compound in the crystal seed preparation use alkali precipitation, and the special crystal seed of ferric oxide is prepared in oxidation at a certain temperature.In the presence of this crystal seed, carry out oxidation with ferrous sulfate and air then, can obtain orange-red ferric oxide, filter again, wash, calcining, superfine grinding finally obtain the pure red accent of high gloss (high brightness) (red maximum mutually) superfine iron oxide red.
The product that this explained hereafter is come out improves gloss and the red degree of ferric oxide red colorant, and this technology is to realize having good environment protecting by the method that reduces influence degree.
Embodiment
Sequence number is 4 in the embodiment 1(table):
Is furnished with stirring at 60 cubic metres, in the reaction container of heating unit and air-distributor, the content of adding after purifying treatment is 30 cubic metres of 5% titanium white by product copperas solutions, then under agitation, add 130 kilograms and 884 kilogram 30% sodium hydroxide of magnesium hydroxide (residual sulfuric acid is ferrous by the sodium hydroxide neutralization) mixing solutions (being diluted to 2.5 cubic metres), the pH that makes solution is that 10(such as pH value are on the low side, available 30% sodium hydroxide solution is finely tuned), after being warming up to 41 degrees centigrade, bubbling air carries out oxidation, the bubbling air amount is 15 cubic meters per minute, during maintain the temperature at 40 to 50 ℃, pH is at 9-10.Stop bubbling air and stirring after 4 hours, crystal seed liquid obtains suspending.This crystal seed suspension pump into 120 cubic metres be furnished with stir and the reaction container of air-distributor in, add 30 cubic metres of 40% the copperas solutions purified, with steam direct heating to 80 ℃, the bubbling air oxidation, and add 10% sodium hydroxide solution, make pH value of solution be stabilized in 3-4.After the oxidation 16 hours, the ferrous surplus in the assaying reaction liquid is 5% when following, stopped reaction.Reaction solution filters, behind the washing leaching cake, the orange red ferric oxide filter cake making beating that obtains, and to pump into diameter be 1.5 meters, length is to calcine in 24 meters the rotary kiln, and control high-temperature zone temperature is 800 ℃, is 60 minutes at kiln residence time. calcination product is after the air at room temperature cooling, carry out superfine grinding with Cyclone mill, obtain ferric oxide red colorant.Surveying this iron oxide red pigment compares with commercially available red iron oxide NS110: △ L:1.76; △ A:1.88.
Attached: the pigment that other example obtains and commercially available red iron oxide NS110 are compared as follows:
(remarks: △ L represents the colour brightness value; △ A represents the color red color tone)
As can be seen from the above table: under the situation that other condition is fixed, along with the increase of magnesium hydroxide in the seed crystal production process (neutralizer is magnesium hydroxide and sodium hydroxide mixing solutions) consumption, iron oxide red brightness (gloss) and red color tone (△ A) can progressively improve simultaneously; But after crystal seed magnesium hydroxide consumption surpassed 140 kilograms, iron oxide red brightness (gloss) and red color tone can obviously descend on the contrary, so the suitable value of above-mentioned crystal seed magnesium hydroxide consumption is about 130 kilograms.In addition, calcining temperature also has considerable influence to iron oxide red brightness (gloss) and red color tone, and its calcining optimal temperature is about 800 ℃.
Claims (2)
1. the preparation method of the pure red accent superfine iron oxide of a high gloss red, being mainly and adopting ferrous sulfate is that raw material is made crystal seed, second oxidation gets ferric oxide under the condition that this crystal seed exists, again to ferric oxide filter, wash, calcine, grind ferric oxide red colorant; It is characterized in that:
Being made as of described crystal seed:
It is 40 ~ 100 g/L solution that refining ferrous sulfate is mixed with concentration, uses NaOH and Mg (OH) then
2Mix in the alkaline solution and above-mentioned solution to pH=9.0 ~ 10.0, the bubbling air oxidation makes crystal seed under 40 ~ 50 ℃ of temperature; Reaction equation is:
FeSO
4+2NaOH=Fe(OH)
?2↓+Na
2SO
4
FeSO
4+?Mg(OH)
?2=Fe(OH)
?2↓+?MgSO
4
2Fe(OH)
2+1/2O
2=2γ-FeOOH+H
2O
Crystal seed transforms: 2 γ-FeOOH → α-Fe
2O
3XH
2O (crystal seed)+H
2O;
Described second oxidation technology is:
Above-mentioned crystal seed is added water latting drown to 1 ~ 1.5 times, adding ferrous sulfate solution to ferrous content is 30 ~ 70g/L, bubbling air carried out oxidation after intensification reached 80 ~ 85 ℃, the ferric oxide that generates is deposited on the above-mentioned nucleus, the sulfuric acid of Sheng Chenging neutralizes with 8% weak ammonia simultaneously, hierarchy of control pH=3.0 ~ 5.0 drip ferrous sulfate and weak ammonia continuously, and nucleus is grown up gradually and formed orange red iron oxide pigment; The second oxidation reaction formula is as follows:
2FeSO
4+1/2O
2+2H
2O=Fe
2O
3·?xH
2O↓+2H
2SO
4?
H
2SO
4+2NH
3?·?H
2O?=(NH
4)
2SO
4?+2H
2O；
Described calcining process is:
With above-mentioned after filtration, the orange red ferric oxide filter cake making beating that obtains after up to standard of washing, and calcine, control high-temperature zone temperature is 800 ℃, calcination time is 60 minutes, calcination product is after the air at room temperature cooling, and superfine grinding finally obtains the pure red accent superfine iron oxide of high gloss red;
The calcination reaction equation is:
。
2. the preparation method of the pure red accent superfine iron oxide of a kind of high gloss according to claim 1 red is characterized in that: Mg (OH) in the mixed alkaline solution of described crystal seed preparation
2With the 30%NaOH mass ratio be 1:20 ~ 1:5.
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| CN102390870B true CN102390870B (en) | 2013-08-28 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217694A (en) * | 2015-08-26 | 2016-01-06 | 昆明理工大学 | A kind of method preparing red iron oxide and ammonium chloride |
| CN107325588A (en) * | 2017-07-10 | 2017-11-07 | 林中 | A kind of preparation method for the pigment for coating high gorgeous degree iron oxide |
| CN108640162B (en) * | 2018-07-10 | 2024-01-09 | 河南省睿博环境工程技术有限公司 | Alkali circulation iron-containing solid waste iron oxide pigment production equipment system |
| CN109354072B (en) * | 2018-09-25 | 2021-05-28 | 河南省睿博环境工程技术有限公司 | Process for harmlessly producing iron oxide red pigment by alkali circulation method |
| CN109133184A (en) * | 2018-09-29 | 2019-01-04 | 德清安凡德新材料科技有限公司 | A kind of preparation method of lithium battery iron oxide red |
| EP3683190B1 (en) * | 2019-01-17 | 2022-03-09 | LANXESS Deutschland GmbH | Method for manufacturing hematite pigments |
| CN111704172A (en) * | 2020-07-09 | 2020-09-25 | 正太新材料科技有限责任公司 | Method for preparing iron oxide red pigment by using calcium carbonate |
| CN113912130B (en) * | 2021-11-29 | 2023-07-07 | 龙佰集团股份有限公司 | Iron oxide red and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143049A (en) * | 1995-05-11 | 1997-02-19 | 山东省五莲钢球总厂 | Technology for producing gulf red oxide by wet process |
| CN1696208A (en) * | 2004-05-14 | 2005-11-16 | 兰克赛斯德国有限公司 | Pure-coloured, readily dispersible iron oxide red pigments with high grinding stability |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143049A (en) * | 1995-05-11 | 1997-02-19 | 山东省五莲钢球总厂 | Technology for producing gulf red oxide by wet process |
| CN1696208A (en) * | 2004-05-14 | 2005-11-16 | 兰克赛斯德国有限公司 | Pure-coloured, readily dispersible iron oxide red pigments with high grinding stability |
Non-Patent Citations (4)
| Title |
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| 李云等.铁泥湿法制备氧化铁红.《沈阳化工学院学报》.2008,第22卷(第2期),105页倒数第一段至106页第3段以及表2、表3. |
| 氨法氧化铁红合成中真实晶核之探讨;蔡传琦;《涂料工业》;20060201;第36卷(第2期);第15-16页 * |
| 蔡传琦.氨法氧化铁红合成中真实晶核之探讨.《涂料工业》.2006,第36卷(第2期),第15-16页. |
| 铁泥湿法制备氧化铁红;李云等;《沈阳化工学院学报》;20080615;第22卷(第2期);第104-106页 * |
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