CN1766005A - Method for preparing high purity iron oxide yellow and iron oxide red using titanium dioxide byproduct ferrous sulfate - Google Patents
Method for preparing high purity iron oxide yellow and iron oxide red using titanium dioxide byproduct ferrous sulfate Download PDFInfo
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Abstract
The invention relates to a method to prepare high-pure iron oxide yellow and iron oxide red by ferrous sulfate as byproduct in titanium white, which comprises: when temperature under 60Deg, refining the material to remove impurity; with oxidant, adjusting pH value of solvent to hydrolyze and remove Ti and co-precipitate to remove metal ion; regulating pH value and feeding air for oxidation at normal temperature; obtaining the products with different reaction conditions. This method is simple, needs low cost and obtains product with high purity.
Description
[ technical field]A method for producing a semiconductor device
The invention relates to a preparation method of iron oxide yellow and iron oxide red, in particular to a method for preparing high-purity iron oxide yellow and iron oxide red by using ferrous sulfate as a titanium dioxide byproduct.
[ background of the invention]
Iron oxide yellow and iron oxide red are common inorganic pigments and are widely applied to the fields of coatings, building materials, plastics, electronics and the like; the high-purity iron oxide red can be used as a polishing agent of optical glass and a high-grade grinding material. The common production methods of iron oxide yellow and iron oxide red mainly comprise the following three methods:
the first preparation method is a copperas calcining method: the method is characterized in that pure copperas is used as a raw material to be calcined at high temperature, and the generated iron oxide red is washed, dried and crushed into a product.
The second preparation method is a wet air oxidation method: the main raw material of the method is iron sheet, the production process is that the seed crystal is prepared by adopting sulfuric acid or nitric acid from the preparation of the seed crystal, the seed crystal is added into a two-step oxidation barrel, the iron sheet and water are added, then ferrous salt is added as a reaction medium, the temperature of steam is raised to be more than 70 ℃, air is blown in for oxidation under the condition of certain pH value, and iron oxide yellow and iron oxide red are obtained.
The third preparation method is an aniline method: the method is to reduce nitrobenzene by scrap iron, and produce iron oxide yellow while producing aniline.
The main raw materials of the wet production method of the iron oxide yellow and the iron oxide red are iron sheet and sulfuric acid, and the production of the iron oxide yellow and the iron oxide red is limited to a certain extent by a raw material route; meanwhile, a large amount of by-product ferrous sulfate is produced in the industrial production of the titanium dioxide by the sulfuric acid method, and the by-product ferrous sulfate is not fully utilized, so that the burden of the production of the titanium dioxide by the sulfuric acid method is caused.
The production of iron oxide yellow and iron oxide red by using ferrous sulfate which is a byproduct in the production of titanium dioxide is reported in China, for example, Chinese patent application No. 02148428.7 discloses a method for producing iron oxide red pigment by using waste ferrous sulfate and waste titanium white, and Chinese patent application No. 02148429.5 discloses a method for producing iron oxide yellow pigment by using waste ferrous sulfate and waste titanium white, wherein the two patents adopt intermediate-temperature (50-70 ℃) iron sheet reduction to control hydrolysis for 6-10 hours, flocculation, sedimentation separation, refined ferrous sulfate heptahydrate and ammonia neutralization to prepare crystalline iron oxide red seed crystal; neutralizing with ammonia water, and oxidizing with air to obtain iron oxide red or yellow pigment.
The main difference of the production process described in various documents and patents is concentrated on the refining and oxidation of ferrous sulfate solution, and other unit operations such as rinsing or washing, filtering and separating, drying and calcining are common operations in chemical production, and the difference is not significant. At present, the process for producing iron oxide yellow and iron oxide red by using titanium dioxide byproducts comprises the following steps:
purification of ferrous sulfate solution: heating a ferrous sulfatesolution to 70-95 ℃, adjusting the pH value of the solution to 1-3.5 by using sulfuric acid, and reducing ferric iron into ferrous iron by using iron sheet to neutralize acidity to obtain a purified ferrous sulfate solution; or obtaining pure ferrous sulfate by a recrystallization mode, and then dissolving to obtain a ferrous sulfate solution.
And (2) two-step oxidation: introducing air to prepare seed crystals under certain conditions, adding the seed crystals into a purified ferrous sulfate solution, heating to above 70 ℃, and introducing air to oxidize ferrous sulfate under certain pH conditions to obtain iron oxide yellow and iron oxide red; then rinsing, filtering, separating, drying and calcining to obtain the iron oxide yellow and the iron oxide red.
The existing various methods for producing iron oxide yellow and iron oxide red by using ferrous sulfate as a byproduct in titanium dioxide production have the following general problems: firstly, in the purification (refining) and oxidation processes, the ferrous sulfate solution needs to be heated to 60-95 ℃, and a large amount of energy is consumed; secondly, iron sheet or waste iron is added in the purification (refining) process, which increases the production cost; thirdly, impurities are not removed completely, and the purity of the produced iron oxide yellow and iron oxide red finished products is not high; fourthly, the seed crystal is prepared in the oxidation process, special equipment is needed, the production process flow is increased, and the investment and the production cost energy are improved; fifthly, the high-purity iron oxide red is produced by reacting pure iron with sulfuric acid, removing impurities through vacuum filtration, adding the obtained ferrous sulfate solution into soda ash, obtaining FeCO3 filter cakes through centrifugal separation, flushing and filtration, and obtaining the ferric oxide with high purity after high-temperature calcination and cyclonecentrifugal crushing. So far, no report of producing high-purity iron oxide yellow and iron oxide red by using ferrous sulfate which is a byproduct in titanium dioxide production is found.
[ summary of the invention]
In order to overcome the defects of heating, incomplete impurity removal, complex production process, high production cost and low product purity of the existing various methods for producing iron oxide yellow and iron oxide red by using a byproduct ferrous sulfate produced by titanium dioxide, the invention provides a method for refining and oxidizing a solution of a byproduct ferrous sulfate of titanium dioxide at normal temperature and producing high-purity iron oxide yellow and iron oxide red.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method mainly comprises the following steps:
the first step is the refining of the ferrous sulfate solution as the by-product of titanium dioxide: the refining process mainly comprises the steps of removing titanium and removing metal ions such as zinc, manganese, aluminum and the like, wherein the pH value of a ferrous sulfate solution is adjusted to be more than 1.5 by adopting water dilution or dilute alkali solution in the titanium removing process, so that titanium ions Ti3+Hydrolysis is complete to form metatitanic acid H2TiO3At a temperature below 60 ℃, coarse-grained metatitanic acid H is formed2TiO3Filtering and separating the ferrous sulfate solution to obtain filtrate which is the ferrous sulfate solution with titanium removed; then removing metal ions such as zinc, manganese, aluminum and the like from the titanium-removed ferrous sulfate solution, adjusting the pH value of the titanium-removed ferrous sulfate solution to be faintly acid by usingan alkaline solution, wherein the pH value is more than 3 and less than 7, adding an oxidant, and oxidizing the ferrous iron in the solution into Fe when oxygen is rich or residual chlorine exists in water or not adding the oxidant to oxidize the ferrous iron in the solution into Fe3+And generating precipitate of ferric hydroxide, wherein the flocculent ferric hydroxide precipitate has strong adsorption capacity to impurity ions, and the impurity ions are coprecipitated and thenFiltering and separating to obtain filtrate which is ferrous sulfate solution with metal ions such as titanium, zinc, manganese, aluminum and the like removed;
the second step is oxidation: adjusting the pH value of the ferrous sulfate solution obtained in the first step, introducing air for oxidation at the temperature of less than 60 ℃, oxidizing ferrous iron into ferric iron, obtaining iron oxide yellow and gradually forming fine iron oxide yellow crystals under the condition that the pH value range is more than 3 and less than 7, obtaining iron oxide red and gradually forming fine iron oxide red crystals under the condition that the pH value range is more than 7 and less than 12, gradually reducing the pH value, controlling the pH value of the solution to be more than 4, continuously introducing air for oxidation, and gradually growing the fine crystals of the iron oxide red to form iron oxide red;
the third step is rinsing, filtration and drying: and (3) adding water to rinse the iron oxide yellow and the iron oxide red obtained in the second step for multiple times until calcium, magnesium and sulfate radicals in the water are qualified, then filtering, and drying the obtained iron oxide yellow and iron oxide red precipitates at 95-110 ℃ to obtain iron oxide yellow and iron oxide red products.
In the first step, under the condition that the generated metatitanic acid is not needed to be used or is little, the two steps of impurity removal of titanium and metal ions such as zinc, manganese, aluminum and the like are combined into one step of impurity removal, and Ti is directly subjected to the second step of impurity removal3+、Fe3+Hydrolysis and precipitation are carried out simultaneously, and a separate titanium removal and separation operation is omitted.
In the first step, the oxidant is hydrogen peroxide, and the adding amount of the hydrogen peroxide is less than 5% of the ferrous sulfate solution according to the volume ratio.
In the first step, the alkaline solution is ammonia water, sodium hydroxide or sodium carbonate.
In the first step, only the titanium removal step is performed when producing iron oxide series pigments of general purity.
In the first step, when the ferric oxide is precipitated, the ferric hydroxide adsorbing impurities is completely precipitated by using activated carbon or a flocculating agent.
Washing metatitanic acid obtained in the first step by using a dilute acid solution, rinsing by using water to remove iron impurities adsorbed on the surface of the crystal, and calcining at a high temperature of 600-800 ℃ to obtain the titanium pigment.
And when the pH value of the alkaline solution is controlled by adopting ammonia water to adjust the alkaline solution in the whole process, the ammonium sulfate contained in the obtained filtrate is concentrated to obtain a byproduct ammonium sulfate.
The invention has the positive effects that: except drying and calcining, all the other steps can be carried out at the normal temperature of lower than 60 ℃, and the energy consumption is low under the normal temperature generally; the two-step impurity removal refining for removing titanium and metal ions such as zinc, manganese, aluminum and the like is adopted, the impurity removal degree is high, and high-purity iron oxide yellow and iron oxide red can be produced; the traditional two-step oxidation method is cancelled, seed crystals do not need to be prepared, air is introduced at normal temperature, and ferrous iron is directly oxidized into iron oxide yellow and iron oxide red, so that the process flow is short and the production cost is low; no waste iron is consumed in the refining process, the cost is reduced, and the resources are saved.
[ description of the drawings]
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic block diagram of the process of the present invention.
In the figure: 1-refining and impurity removal, 11-titanium removal, 12-removal of metal ions such as zinc, manganese, aluminum and the like, 2-oxidation, 3-rinsing, filtering and drying, and 4-calcination.
[ detailed description]embodiments
Example 1:
a process for preparing high-purity iron oxide yellow and red oxide from the ferrous sulfate as by-product of titanium white features that the concentration of ferrous sulfate is 20%, and the ferrous sulfate as by-product contains ferrous sulfate as main component and Mg, Al, Si, Ca, Ti, Zn, Ba, Mn, etc. These elements have a great influence on the production of iron oxide yellow and iron oxide red, so the first step is the purification of the ferrous sulfate solution 1:
in the refining 1, there are two steps of impurity removal and separation, in this example, the two stepsof impurity removal are both carried out at room temperature, the first step of impurity removal and separation is to remove titanium 11 and other impurities, the pH value of the solution is adjusted to be more than 1.5 by water dilution or dilute alkali solution, so that the Ti ion Ti is obtained3+Hydrolysis is complete to form metatitanic acid H2TiO3The principle of hydrolysis can be expressed as:
under the condition of heating, metatitanic acid H2TiO3The hydrolysis reaction is rapid; hydrolysis reaction time at room temperatureLonger, but coarser particles are produced, which are easily filtered. After hydrolysis at a temperature lower than 60 ℃, in this example, filtration separation is performed at room temperature, and the obtained filtrate is a ferrous sulfate solution from which titanium is removed.
The second step of impurity removal is to remove metal ions 12 such as zinc, manganese, titanium and the like, certainly, after most of titanium is removed in the first step of refining impurity removal 11, a small amount of ultrafine crystals of metatitanic acid exist in the solution and need to be further removed, the pH value of the filtrate after titanium removal and refining 11 is adjusted to 5.5 by concentrated ammonia water, and a small amount of hydrogen peroxide is added or air is introduced to oxidize a small amount of ferrous iron in the solution into Fe3+And (3) generating iron hydroxide precipitate, wherein the flocculent iron hydroxide precipitate has strong adsorption capacity on impurity ions during precipitation, and most impurity ions are subjected to coprecipitation. Since little ferric hydroxide is formed and is easy to be gelatinous, the ferric hydroxide adsorbing impurities can be completely precipitated by using activated carbonor a flocculating agent, and the filtering is easier when the activated carbon is used in the embodiment.
In the present refining 1, if the metatitanic acid produced is not used or is very little, the two steps may be combined into one step, and Ti may be directly added under the conditions of the second step 123+And Fe3+Hydrolysis and precipitation are carried out simultaneously, and 1 separation operation can be omitted. In the case of producing a general purity iron oxide series pigment, only the step of removing titanium 11 may be operated.
The second step is oxidation: experiments show that the oxidation can be carried out without adding seed crystals, and when newly prepared seed crystals exist, the generated ferric hydroxide particles can be uniform, the oxidation speed is also influenced to a certain extent, but the operation steps are increased, and the cost is increased.
In order to reduce the working procedures, seed crystals are not added into the ferrous sulfate solution, the pH value of the solution is adjusted, the pH value is adjusted to be 5-7 by using concentrated ammonia water, air is introduced at room temperature for oxidation 2, the pH value is gradually reduced, the pH value is controlled to be 3-7, air is continuously introduced, and iron oxide yellow crystals grow gradually to obtain iron oxide yellow precipitates; the iron oxide yellow is converted into iron oxide red after being calcined at the temperature of 300 ℃, and the purity reaches 99.5 percent.
In the process of oxidizing 2, air is introduced for oxidizing 2 under different pH conditions at the temperature of less than 60 ℃, so that ferric iron is hydrolyzed to obtain different products: under the weak acidic condition, the pH value range is 3-7, the obtained iron oxide yellow is, and under the alkaline condition, the pH value range is 7-12, the obtained iron oxide red is. Due to H produced during hydrolysis of ferric iron+Ions to gradually increase the acidity of the solution, and an alkaline aqueous solution is required to be continuously added in the production process to control the pH value of the solution to be more than 3 in the oxidation reaction process.
The third step is rinsing, filtering and drying 3: and (3) adding water to rinse the iron oxide yellow and the iron oxide red obtained in the steps for multiple times until calcium, magnesium, sulfate radical and the like in the water are qualified, filtering, and drying the obtained iron oxide yellow and iron oxide red precipitate at 95-110 ℃ to obtain iron oxide yellow and iron oxide red products. The iron oxide yellow is stable when being dried below 120 ℃, and can be converted into iron oxide red when being heated to above 260 ℃.
In order to comprehensively utilize ferrous sulfate as a byproduct of titanium dioxide, metatitanic acid H is obtained in the dissolving and purifying processes of the invention2TiO3Washing with dilute acid solution, rinsing with water to remove impurities such as iron adsorbed on the crystal surface, and calcining at 600-800 ℃ to obtain the high-quality titanium pigment.
Meanwhile, if the alkaline solution is adjusted by ammonia water to control the pH value of the solution, the obtained filtrate contains a large amount of ammonium sulfate, and the ammonium sulfate solution can be concentrated to obtain a byproduct ammonium sulfate.
Example 2:
the concentration of ferrous sulfate in this example was 1 mol. L-1Directly adjusting the pH value to 5.5 by using a concentrated NaOH solution after dissolution to hydrolyze titanium and ferric iron in the solution, filtering, performing impurity removal refining 1, adjusting the pH value of the filtrate subjected to the impurity removal refining 1 to 3-7 by using a 20% NaOH solution to obtain a dark green ferrous sulfate colloid of the solution, and introducing air to the colloid for oxidation 2 under the condition that the temperature is lower than 60 ℃ to obtain iron oxide yellow; the iron oxide yellow is calcined at the temperature of 300 ℃ for 4 ℃ and then converted into iron oxide red with the purity of more than 96 percentThe national standard for preparing iron oxide red by sulfuric acid method.
Under the condition that the temperature is lower than 60 ℃, refining and impurity removal are carried out on a ferrous sulfate solution as a titanium dioxide byproduct, the purposes of removing titanium and removing metal ions such as zinc, manganese and the like are achieved by adjusting the pH value of the solution, then the pH value of the solution is controlled, air is introduced for oxidation under the normal temperature condition, and iron oxide yellow or iron oxide red is obtained under different reaction conditions; the iron oxide yellow is converted into iron oxide red after being calcined at the temperature of 300 ℃, and the purity reaches 99.5 percent. The method has the advantages of simple process flow, low manufacturing cost and high purity of the obtained product, and is suitable for comprehensive utilization of the ferrous sulfate as a titanium dioxide byproduct.
Claims (8)
1. A method for preparing high-purity iron oxide yellow and iron oxide red by using a titanium dioxide byproduct ferrous sulfate is characterized by comprising the following steps of: the method mainly comprises the following steps:
the first step is the refining of the ferrous sulfate solution as the by-product of titanium dioxide: the refining process mainly comprises the steps of removing titanium and removing metalions such as zinc, manganese, aluminum and the like, wherein the pH value of a ferrous sulfate solution is adjusted to be more than 1.5 by adopting water dilution or dilute alkali solution in the titanium removing process, so that titanium ions Ti3+Hydrolysis is complete to form metatitanic acid H2TiO3At a temperature below 60 ℃, coarse-grained metatitanic acid H is formed2TiO3Filtering and separating the ferrous sulfate solution to obtain filtrate which is the ferrous sulfate solution with titanium removed; then removing metal ions such as zinc, manganese, aluminum and the like from the titanium-removed ferrous sulfate solution, adjusting the pH value of the titanium-removed ferrous sulfate solution to be faintly acid by using an alkaline solution, wherein the pH value is more than 3 and less than 7, adding an oxidant to oxidize ferrous iron in the solution into Fe3+And generating ferric hydroxide precipitate, wherein the flocculent ferric oxide precipitate has strong adsorption capacity on impurity ions during precipitation, the impurity ions generate coprecipitation, and then filtering and separating are carried out to obtain filtrate which is ferrous sulfate solution from which metal ions such as titanium, zinc, manganese, aluminum and the like are removed;
the second step is oxidation: adjusting the pH value of the ferrous sulfate solution obtained in the first step, introducing air for oxidation at the temperature of less than 60 ℃, oxidizing ferrous iron into ferric iron, obtaining iron oxide yellow and gradually forming fine iron oxide yellow crystals under the condition that the pH value range is more than 3 and less than 7, obtaining iron oxide red and gradually forming fine iron oxide red crystals under the condition that the pH value range is more than 7 and less than 12, gradually reducing the pH value, and then controlling the pH value of the solution to be more than 4, and gradually growing the fine crystals of the iron oxide red to form iron oxide red;
the third step is rinsing, filtration and drying: and (3) adding water to rinse the iron oxide yellow and the iron oxide red obtained in the second step for multiple times until calcium, magnesium and sulfate radicals in the water are qualified, then filtering, and drying the obtained iron oxide yellow and iron oxide red precipitates at 95-110 ℃ to obtain iron oxide yellow and iron oxide red products.
2. The method for preparing high-purity iron oxide yellow and iron oxide red by using the ferrous sulfate as the titanium dioxide byproduct according to claim 1, which is characterized by comprising the following steps of: in the first step, under the condition that the generated metatitanic acid is not needed to be used or is little, the two steps of impurity removal of titanium and metal ions such as zinc, manganese, aluminum and the like are combined into one step of impurity removal, and Ti is directly subjected to the second step of impurity removal3+、Fe3+Hydrolysis and precipitation are carried out simultaneously, and a separate titanium removal and separation operation is omitted.
3. The method for preparing high-purity iron oxide yellow and iron oxide red by using the ferrous sulfate as the titanium dioxide byproduct according to claim 1 or 2, which is characterized by comprising the following steps of: in the first step, only the titanium removal step is performed when producing iron oxide series pigments of general purity.
4. The method for preparing high-purity iron oxide yellow and iron oxide red by using the ferrous sulfate as the titanium dioxide byproduct according to claim 1 or 2, which is characterized by comprising the following steps of: in the first step, the oxidant is hydrogen peroxide or sodium nitrite, and the adding amount of the hydrogen peroxide is less than 5 percent of the ferrous sulfate solution according to the volume ratio.
5. The method for preparing high-purity iron oxide yellow and iron oxide red by using the ferrous sulfate as the titanium dioxide byproduct according to claim 1, which is characterized by comprising the following steps of: and in the first step, when the ferric hydroxide is precipitated, activated carbon or a flocculating agent is used for completely precipitating the ferric hydroxide adsorbing impurities.
6. The method for preparing high-purity iron oxide yellow and iron oxide red by using the ferrous sulfate as the titanium dioxide byproduct according to claim 1, which is characterized by comprising the following steps of: in the first step, the alkaline solution is ammonia water or sodium hydroxide.
7. The method for preparing high-purity iron oxide yellow and iron oxide red by using the ferrous sulfate as the titanium dioxide byproduct according to claim 1 or 2, which is characterized by comprising the following steps of: washing metatitanic acid obtained in the first step by using a dilute acid solution, rinsing by using water to remove iron impurities adsorbed on the surface of the crystal, and calcining at a high temperature of 600-800 ℃ to obtain the titanium pigment.
8. The method for preparing high-purity iron oxide yellow and iron oxide red by using the ferrous sulfate as the titanium dioxide byproduct according to claim 1 or 5, which is characterized by comprising the following steps of: and when the pH value of the alkaline solution is controlled by adopting ammonia water to adjust the alkaline solution in the whole process, the ammonium sulfate contained in the obtained filtrate is concentrated to obtain a byproduct ammonium sulfate.
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