CN108726575B - Method for preparing nano ferric oxide iron oxide red by using rutile mother liquor as raw material - Google Patents
Method for preparing nano ferric oxide iron oxide red by using rutile mother liquor as raw material Download PDFInfo
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Abstract
The invention relates to a method for preparing a rutile mother liquorThe method for preparing the nano ferric oxide iron oxide red by the raw materials comprises the following steps: (1): taking rutile mother liquor, and sequentially adding a dispersing agent and a precipitating agent into the rutile mother liquor to obtain a precipitate iron oxide red precursor; (2): and (2) transferring the iron oxide red precursor in the step (1) into a hydrothermal reactor, carrying out hydrothermal reaction, filtering, washing and drying to obtain a nano iron oxide red product. Compared with the prior art, the invention utilizes the chemical engineering technology, the nanotechnology and the mesoscale regulation and control method to prepare the series of high-added-value nano Fe2O3The iron oxide red product has simple synthesis process, is easy to prepare in large scale, has the color from light red to dark brown red, and provides a choice for users to select new products. The technology of the invention has important significance for updating the traditional powder metallurgy enterprise technology, breaking through foreign high-end iron oxide red technical blockade and promoting clean utilization of resources in China.
Description
Technical Field
The invention belongs to the technical field of preparation of nano iron oxide red, and relates to a method for preparing nano iron oxide red by using rutile mother liquor as a raw material.
Background
The artificial rutile is a titanium-rich raw material which is obtained by separating most of iron components in titanium concentrate by using a chemical method and has the same components and structural properties as natural rutile, and the main component of the raw material is TiO2The content fluctuates between 91 and 96%. Generally, titanium and iron in titanium concentrate have high content, the proportion is close to about 1:1, and the titanium concentrate also contains a small amount of impurities such as manganese, chromium and the like, and in the production process of the artificial rutile, a large amount of iron in the titanium concentrate enters a solution in the form of ferrous iron or ferric iron to form a large amount of rutile mother liquor.
The traditional technical method is to prepare Fe by the technological processes of concentration, crystallization, purification, ammonium bicarbonate double hydrolysis, coating, calcination and the like of rutile mother liquor2O3Iron oxide red pigment. The traditional technical method has the defects of complex technical route, high cost and Fe preparation2O3Poor color and luster of the iron oxide red product, low composition content and the like. Fe prepared by conventional method2O3Iron oxide red products are mostly low-end Fe2O3The price of the iron red product is 3000-5000 yuan/ton, and the production cost sometimes reaches about 5500-6000 yuan/ton.
Therefore, since a large amount of rutile mother liquor is produced during the production of synthetic rutile, the rutile mother liquor cannot be directly discharged according to the national wastewater discharge standard if low-end Fe is prepared according to the conventional technical method2O3Iron oxide red products, enterprises face the situation of loss and embarrassment. Meanwhile, the high-end iron oxide red production technology is mainly mastered by several foreign major companies(e.g., Bayer, Germany, Ferzium, and Reichard, USA, etc.), the cost is very high if foreign technologies are introduced.
The invention ZL201310111493.1 of China discloses a method for processing artificial rutile mother liquor, which comprises the steps of heating and pre-concentrating the artificial rutile mother liquor to ensure that Fe in the mother liquor is3+After the concentration is increased to more than 150g/L, the mixed iron source reacts in a fluidized bed reactor filled with HCl gas to increase the iron concentration of mother liquor, then the acidolysis solution is filtered, frozen and crystallized to obtain ferric trichloride crystals, and finally the crystals are roasted to obtain high-grade iron oxide red. The method for preparing the iron oxide red by adopting the rutile mother liquor still has the problems of complex preparation process and low process stability.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing nano ferric oxide red by taking rutile mother liquor as a raw material, which adopts a chemical engineering technology, a nanotechnology and a mesoscale regulation and control method and takes industrial rutile mother liquor as a raw material to prepare high-end nano Fe2O3The iron oxide red product breaks through foreign technology blockade, makes full use of iron element in rutile mother liquor, accords with sustainable development and green environmental protection production strategies, and has important significance for technology updating, new product research and development and market demand meeting of traditional artificial rutile production enterprises.
The purpose of the invention can be realized by the following technical scheme:
the invention aims to provide a method for preparing nano ferric oxide iron oxide red by taking rutile mother liquor as a raw material, which comprises the following steps in sequence:
(1): taking rutile mother liquor, and sequentially adding a dispersing agent and a precipitating agent into the rutile mother liquor to obtain a precipitate iron oxide red precursor;
(2): and (2) transferring the iron oxide red precursor in the step (1) into a hydrothermal reactor, carrying out hydrothermal reaction, filtering, washing and drying to obtain a nano iron oxide red product.
Further, in the step (1), the rutile mother liquor is prepared by the following method:
(A) the method comprises the following steps Calcining the industrial titanium concentrate, cooling to room temperature, then placing the industrial titanium concentrate in a reducing gas atmosphere for reduction, and after the reaction is finished, isolating air and cooling to room temperature to obtain oxidation/reduction modified titanium concentrate;
(B) the method comprises the following steps And (C) adding the titanium concentrate subjected to oxidation/reduction modification in the step (A) into dilute hydrochloric acid, heating, controlling condensation reflux and stirring for reaction, cooling to room temperature after the reaction is finished, and filtering the obtained solution to obtain the rutile mother liquor.
Further, in the step (a), the calcination process conditions are as follows: calcining at 950-1050 deg.C for 4-6 h;
the reduction process conditions are as follows: reducing for 4h at 850-950 ℃.
Furthermore, the reducing gas is hydrogen, and the introduction amount of the reducing gas is 5.5 g/batch of industrial titanium concentrate, and the industrial titanium concentrate is 60 g/batch.
Furthermore, in the step (B), the dilute hydrochloric acid is 20-25% of dilute hydrochloric acid, and the mass ratio of the oxidation/reduction modified titanium concentrate to the dilute hydrochloric acid is 1: 5.
Further, in the step (B), the specific conditions for raising the temperature and stirring the reaction are as follows: stirring for 10-24h at 95-105 deg.C and stirring speed of 800-1000 rpm.
Further, in the step (1), the dispersant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, triblock copolymer F127 and polyethylene glycol;
the precipitant is one or more of ammonia water, sodium carbonate, sodium bicarbonate and sodium hydroxide.
Further, in the step (1), the concentration of the precipitating agent is 1-10M, and the addition amount of the precipitating agent satisfies the following condition: the volume ratio of the rutile mother liquor to the precipitator is 1: 3-8;
the concentration of the dispersant (i.e. the surfactant) is 0.01-0.1M, and the addition amount thereof satisfies: the volume ratio of the rutile mother liquor to the dispersant is 100: 1.
Further, in the step (1), the pH value of the solution is controlled to be between 3.0 and 8.5.
Further, the conditions of the hydrothermal reaction in the step (2) are as follows: the temperature is 150-220 ℃, and the time is 1-3 h.
The preparation of the rutile mother liquor is carried out according to the current industrial production technical route, and is a method and a procedure for simulating real industrial production of the rutile mother liquor, so that the technical method can be better linked with industry, and is convenient for industrial application. The main component of the obtained rutile mother liquor is FeCl2And FeCl3After the surfactant is added, the molecules of the surfactant contain lone-pair electrons and can be complexed with empty orbitals of iron elements, so that the rutile mother liquor can be dispersed from molecular and atomic levels, a precipitator is added to obtain a dispersed iron red precursor, the dosage of the surfactant is related to the content of iron ions in the rutile mother liquor, the concentration of the surfactant used in the invention is 0.01-0.1M, the volume ratio of the surfactant to the rutile mother liquor is 1:100, and the application range of the surfactant can effectively disperse the iron ions in the solution. If the dosage of the surfactant is too low, the molecules of the surfactant cannot effectively disperse iron ions of the system, and the prepared iron oxide red product has serious agglomeration phenomenon; if the dosage of the surfactant is higher, on one hand, the industrial production cost is increased, on the other hand, after the iron oxide red product is prepared, a large amount of water is needed for washing the iron oxide red product, and a large amount of the surfactant in the washing liquid needs to be further treated to be discharged, so that the enterprise cost is further increased. The concentration of the precipitant used in the invention is 1-10M, the volume ratio of the rutile mother liquor to the precipitant is 1:3-8, the pH value of the solution is controlled between 3.0-8.5, the purity of the prepared nano iron red product can reach more than 99.0 percent, and if the concentration is not in the range required by the invention, the purity of the product is lower. The iron oxide red precursor can generate decomposition reaction through hydrothermal reaction (the temperature is 150-220 ℃ and the time is 1-3h) to generate nano iron oxide red (Fe)2O3) And (5) producing the product. The iron oxide red precursor is subjected to decomposition reaction under hydrothermal condition, and the color and luster of the iron oxide red product and Fe2O3The crystallinity of the nano iron red product is related to the factor of the micro-microstructure, and the crystallinity and the micro-microstructure of the prepared nano iron red product are different by regulating and controlling the hydrothermal reaction temperature (150-220 ℃) and the addition amount of the precipitator, so that the colors of the iron red are different, and the change of the color of the nano iron red from dark red to light red is realized。
The high-quality iron oxide red material is obtained in a complex solid/liquid/gas three-phase hydrothermal system, and a reaction system has multiple-level mesoscale behaviors of typical material surface interface, precursor phase change, decomposition and fusion, complex system integration and the like. Individual elements such as iron oxide precursors, organic molecules and anions have multi-level mesoscale behaviors such as individual element mutual transmission, reaction coupling and material surface interface behavior in a complex hydrothermal system, so that the size, the appearance, the structure and the color of the iron oxide red material are different, and the full play of the macroscopic superiority of the iron oxide red material is influenced. The invention prepares a series of high-quality iron oxide red products by comprehensively considering the phase change, hydrothermal growth habit, hydration and ion induction effect of a precursor and the surface interface reaction-diffusion orientation control rule of an iron-based hybrid and by utilizing a chemical engineering technology, a nanotechnology and a mesoscale regulation and control method.
Compared with the prior art, the invention has the following characteristics:
(1) industrial rutile mother liquor is used as a raw material, a chemical engineering technology, a nanotechnology and a mesoscale regulation and control method are utilized to prepare a series of high-quality iron oxide red products, and the color and the composition of the iron oxide red products are comparable to those of Bayer 4130 iron oxide red products;
(2) prepared series of nano Fe2O3The color of the iron oxide red product is from light red to dark brown red, the purity of the product is over 99.0 percent, the prepared iron oxide red has high crystallinity, and the dispersibility of aqueous solution is superior to that of Bayer 4130 iron oxide red products;
(3) the method is suitable for preparing series of iron oxide red products with high added value by taking the rutile mother liquor as the raw material, the used technical method is simple and effective, most of iron elements in the rutile mother liquor can be utilized, and the method has the advantages of low preparation cost, low energy consumption, simple reaction equipment, stable production process, easiness in large-scale production and the like.
Drawings
FIG. 1 is a schematic diagram of a preparation process of the present invention;
FIG. 2 shows the nano Fe prepared by the present invention2O3Iron oxide red series products and Bayer 4130 iron oxide redComparative photographs of powder samples;
FIG. 3 shows nano Fe prepared by the invention2O3Optical photographs of iron oxide red series products and Bayer 4130 iron oxide red powder samples after being dispersed in aqueous solution;
FIG. 4 shows nano Fe prepared by the invention2O3Optical photos of iron oxide red series products and Bayer 4130 iron oxide red powder samples after being dispersed in aqueous solution for 1 hour;
FIG. 5 shows nano Fe prepared by the invention2O3Optical photos of iron oxide red series products and Bayer 4130 iron oxide red powder samples after being dispersed in aqueous solution for 18 hours;
FIG. 6 shows the preparation of nano-Fe2O3Scanning Electron Microscope (SEM) photograph of iron red product 1;
FIG. 7 shows the preparation of nano-Fe according to the present invention2O3SEM photograph of iron red product 2;
FIG. 8 shows the nano Fe prepared by the present invention2O3SEM photograph of iron red product 3;
FIG. 9 shows the nano-Fe prepared by the present invention2O3SEM photograph of iron red product 4;
FIG. 10 shows the preparation of nano-Fe according to the present invention2O3Transmission Electron Microscope (TEM) photograph of iron red product 4;
FIG. 11 is an SEM photograph of a Bayer 4130 iron red product;
FIG. 12 Nano Fe prepared with addition of lower amount of dispersant2O3SEM photograph of iron red product.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The invention provides a method for preparing nano ferric oxide iron oxide red by taking rutile mother liquor as a raw material, which comprises the following steps in sequence:
(1): taking rutile mother liquor, and sequentially adding a dispersing agent and a precipitating agent into the rutile mother liquor to obtain a precipitate iron oxide red precursor;
(2): and (2) transferring the iron oxide red precursor in the step (1) into a hydrothermal reactor, carrying out hydrothermal reaction, filtering, washing and drying to obtain a nano iron oxide red product.
In a preferred embodiment of the present invention, in step (1), the rutile mother liquor is prepared by the following method:
(A) the method comprises the following steps Calcining the industrial titanium concentrate, cooling to room temperature, then placing the industrial titanium concentrate in a reducing gas atmosphere for reduction, and after the reaction is finished, isolating air and cooling to room temperature to obtain oxidation/reduction modified titanium concentrate;
(B) the method comprises the following steps And (C) adding the titanium concentrate subjected to oxidation/reduction modification in the step (A) into dilute hydrochloric acid, heating, controlling condensation reflux and stirring for reaction, cooling to room temperature after the reaction is finished, and filtering the obtained solution to obtain the rutile mother liquor.
In a further preferred embodiment, in step (a), the calcination process conditions are: calcining at 950-1050 deg.C for 4-6 h;
the reduction process conditions are as follows: reducing for 4h at 850-950 ℃.
In a further preferred embodiment, the reducing gas is hydrogen, which is fed in an amount of 5.5g per batch of industrial titanium concentrate, which is 60g per batch.
In a further preferred embodiment, in step (B), the dilute hydrochloric acid is 20-25% dilute hydrochloric acid, and the mass ratio of the oxidation/reduction-modified titanium concentrate to the dilute hydrochloric acid is 1: 5.
In a more preferred embodiment, in step (B), the specific conditions for raising the temperature and stirring the reaction are as follows: stirring for 10-24h at 95-105 deg.C and stirring speed of 800-1000 rpm.
In a preferred embodiment of the present invention, in step (1), the dispersant is one or more selected from cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, triblock copolymer F127 and polyethylene glycol.
In a preferred embodiment of the invention, the precipitant is one or more of ammonia water, sodium carbonate, sodium bicarbonate and sodium hydroxide.
In a preferred embodiment of the present invention, in the step (1), the concentration of the precipitant is 1 to 10M, and the amount added is such that: the volume ratio of the rutile mother liquor to the precipitator is 1: 3-8.
In a preferred embodiment of the present invention, the concentration of the dispersant (i.e., surfactant) is 0.01 to 0.1M, and the amount added is such that: the volume ratio of the rutile mother liquor to the dispersant is 100: 1.
In a preferred embodiment of the present invention, in step (1), the pH of the solution is controlled to be between 3.0 and 8.5.
In a preferred embodiment of the present invention, the conditions of the hydrothermal reaction in step (2) are: the temperature is 150-220 ℃, and the time is 1-3 h.
The present invention will be further described with reference to the following examples.
Example 1
As shown in figure 1, the method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (980 ℃ for 5h), naturally cooling to room temperature after calcination, reducing the oxidized industrial titanium concentrate for 4h at 900 ℃ in a hydrogen atmosphere, adding 22% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 102 ℃, condensing and refluxing, mechanically stirring for 15h at the stirring speed of 900 r/min, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are divalent iron salt and trivalent iron salt.
500mL of the prepared rutile mother liquor is measured, 5mL (0.05M) of hexadecyl trimethyl ammonium bromide and 2000mL of sodium hydroxide (2M) precipitator are sequentially added, the pH value of the solution is controlled to be 3.0-8.5, most of iron ions in the solution are precipitated, and the obtained precipitate is an iron oxide red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (210 ℃, 2h), filtering, washing and drying to obtain an iron oxide red 1 product.
Example 2
As shown in figure 1, the method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (980 ℃ for 5h), naturally cooling to room temperature after calcination, reducing the oxidized industrial titanium concentrate for 4h at 900 ℃ in a hydrogen atmosphere, adding 22% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 102 ℃, condensing and refluxing, mechanically stirring for 15h at the stirring speed of 900 r/min, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are divalent iron salt and trivalent iron salt.
500mL of the prepared rutile mother liquor is measured, 5mL (0.05M) of hexadecyl trimethyl ammonium bromide and 2000mL of sodium hydroxide (4M) precipitator are sequentially added, the pH value of the solution is controlled to be 3.0-8.5, most of iron ions in the solution are precipitated, and the obtained precipitate is an iron oxide red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (at 180 ℃ for 2h), filtering, washing and drying to obtain an iron oxide red 2 product.
Example 3
As shown in figure 1, the method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (980 ℃ for 5h), naturally cooling to room temperature after calcination, reducing the oxidized industrial titanium concentrate for 4h at 900 ℃ in a hydrogen atmosphere, adding 22% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 102 ℃, condensing and refluxing, mechanically stirring for 15h at the stirring speed of 900 r/min, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are divalent iron salt and trivalent iron salt.
500mL of the prepared rutile mother liquor is measured, 5mL (0.05M) of hexadecyl trimethyl ammonium bromide and 2000mL of sodium hydroxide (8M) precipitator are sequentially added, the pH value of the solution is controlled to be 3.0-8.5, most of iron ions in the solution are precipitated, and the obtained precipitate is an iron oxide red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (180 ℃, 2h), filtering, washing and drying to obtain an iron oxide red 3 product.
Example 4
As shown in figure 1, the method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (980 ℃ for 5h), naturally cooling to room temperature after calcination, reducing the oxidized industrial titanium concentrate for 4h at 900 ℃ in a hydrogen atmosphere, adding 22% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 102 ℃, condensing and refluxing, mechanically stirring for 15h at the stirring speed of 900 r/min, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are divalent iron salt and trivalent iron salt.
500mL of the prepared rutile mother liquor is measured, 5mL (0.05M) of hexadecyl trimethyl ammonium bromide and 2000mL of sodium hydroxide (10M) precipitator are sequentially added, the pH value of the solution is controlled to be 3.0-8.5, most of iron ions in the solution are precipitated, and the obtained precipitate is an iron oxide red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (at 150 ℃ for 2h), filtering, washing and drying to obtain an iron oxide red 4 product.
The optical photograph of the synthesized series of nano iron oxide red and Bayer 4130 iron oxide red products is shown in FIG. 2 (a). The resultant iron oxide red product 1 is seen to be dark red in fig. 2(a), the resultant iron oxide red 4 is seen to be light red in fig. 2(d), and the resultant iron oxide red 2 and 3 is seen to be between dark red and light red in fig. 2(b) and 2(c), and is very close in color to bayer 4130 iron red (fig. 2 (e)). In order to verify the dispersion difference between the synthesized iron oxide red and Bayer 4130 iron oxide red products, the prepared systemThe column iron oxide red sample and the bayer 4130 iron oxide red sample were essentially dispersed in aqueous solution, as shown in fig. 3. As can be seen from FIG. 3, both the synthetic iron oxide red products and the Bayer 4130 iron oxide red products were well dispersed in the aqueous solution. After the iron oxide red solution is kept stand for 1h (figure 4), it can be seen that the prepared iron oxide red series products have no solid-liquid separation phenomenon, the Bayer 4130 iron oxide red products have slight solid-liquid separation sign, and the upper layer of the solution is in a semitransparent state. When the iron oxide red solution is allowed to stand for 18h (figure (5)), the upper solution of the prepared series of iron oxide red products also appears semi-transparent, and the upper solution of the Bayer 4130 iron oxide red products becomes very clear. The iron oxide red solution standing experiment result shows that the dispersibility of the synthesized iron oxide red series products in the aqueous solution is superior to that of Bayer 4130 iron oxide red products. SEM photographs of the prepared iron red product 1 (figure 6), the iron red product 2 (figure 7), the iron red product 3 (figure 8) and the iron red product 4 (figure 9) show that the synthesized series of iron red products have the particle size of about 200nm, spherical shapes and good product dispersibility. FIG. 10 shows the preparation of nano-Fe according to the present invention2O3TEM photograph of iron red product 4. As can be seen from FIG. 10, the synthesized nano Fe2O3The crystal lattice stripes of the iron oxide red product are very clear, and the iron oxide red product has higher crystallinity. As is well known, Fe2O3The crystallinity of the nano material is improved along with the increase of hydrothermal temperature, the reaction temperature of the invention is between 150 and 220 ℃, and the invention can ensure the synthesized series of nano Fe2O3The iron oxide red product has higher crystallinity, and the overhigh hydrothermal reaction temperature can increase the production cost on one hand, and can also have more strict requirements on reaction equipment on the other hand, thereby bringing potential production safety problems. SEM photographs of the bayer 4130 iron red product are shown in fig. 11. As can be seen from fig. 11, the bayer 4130 iron oxide red product is composed of a large number of particles of about 100-200nm, but the agglomeration phenomenon between the particles is very serious, and the agglomeration between the particles causes the formation of agglomerates with larger size, and thus the precipitates are easily generated in the aqueous solution. The SEM photo of the iron oxide red product is consistent with the iron oxide red standing experiment result, the series of iron oxide red products synthesized by the method has good dispersibility, and the agglomeration phenomenon of the Bayer 4130 iron oxide red product is more serious, so that the Bayer 4130 iron oxide red product is more obvious after standing for 18 hoursThe solid-liquid separation phenomenon.
Table 1 shows nano Fe prepared by the present invention2O3X-ray fluorescence spectroscopy (XRF) analysis of the iron red line products and bayer 4130 iron red powder samples.
TABLE 1
As can be seen from table 1, the purity of the synthesized iron oxide red product 1, iron oxide red product 2, iron oxide red product 3 and iron oxide red product 4 is 99.1607%, 99.0629%, 99.1300% and 99.1215%, respectively, while the purity of the bayer 4130 iron oxide red product is 99.2944%, which is slightly higher than that of the synthesized iron oxide red product. The results of the color and luster of the synthesized iron oxide red product, the aqueous solution dispersion experiment, the SEM morphology observation and the XRF composition analysis experiment prove that the series of iron oxide red products synthesized by the method have comparability with Bayer 4130 iron oxide red products, and have important significance for the comprehensive utilization of resources in China.
When the addition amount of the dispersing agent is 0.005M (the concentration of the dispersing agent is 0.01-0.1M) and the volume ratio of the dispersing agent to the rutile mother liquor is 1:100, the prepared nano Fe2O3The SEM photograph of the iron red product is shown in fig. 12. As can be seen from fig. 12, the lower amount of surfactant was not able to effectively disperse nano Fe2O3The product has very serious agglomeration phenomenon, the particles are mutually agglomerated to form agglomerates with larger size, and Fe2O3The particle size is also not uniform. Therefore, outside the range of the dispersant of the present invention, highly dispersed nano-Fe cannot be prepared2O3Iron oxide red product. The hydrothermal reaction temperature is 150-220 ℃ and the time is 1-3h, so that the iron oxide red precursor can be completely decomposed into Fe after the hydrothermal reaction2O3. When the precursor was treated at 140 deg.C (reaction 3h), the product and precursor were found to be very close in appearance after the reaction was complete, rather than Fe2O3The red color characteristic is required, and we can judge that the iron oxide red precursor can not be completely decomposed into Fe under the condition of lower reaction temperature2O3. The invention relates to a rutile motherThe volume ratio of the liquid to the precipitator is controlled to be 1:3-8, when the volume ratio of the liquid to the precipitator is less than 1:3, most of iron ions in the rutile mother liquor can not be precipitated, and when the volume ratio of the liquid to the precipitator is more than 1:8, the purity of the prepared iron oxide red product is obviously reduced. For example, when the volume ratio of the rutile mother liquor to the precipitator is adjusted to 1:8.2, the prepared nano Fe2O3The XRF analysis of the iron red product is shown in table 2. As can be seen from Table 2, when the concentration of the precipitant is higher than the required range, the purity of the obtained iron oxide red product is lower, and the prepared iron oxide red product has a poor color due to the higher content of impurities. If the conditions are not under the key treatment conditions, the high-value-added iron red product with high crystallinity, high purity and high water solution dispersibility cannot be obtained. Therefore, the method has obvious innovativeness in the aspects of process steps and the like.
TABLE 2
| Analyte | Fe2O3 | Al2O3 | V2O5 | Co2O3 | Mn2O3 | ZnO |
| Content (wt.) | 86.6824％ | 4.0935％ | 3.5865％ | 1.5214％ | 1.3172％ | 1.1026％ |
| Analyte | Cr2O3 | PbO | TiO2 | Cl | ||
| Content (wt.) | 0.5675％ | 0.5123％ | 0.3587％ | 0.2579％ |
Example 5
As shown in figure 1, the method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (1050 ℃, 4 hours), naturally cooling to room temperature after calcination, reducing the oxidized industrial titanium concentrate for 4 hours at 850 ℃ in a hydrogen atmosphere, adding 20% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 95 ℃, condensing and refluxing, mechanically stirring for 24 hours at the stirring speed of 800 revolutions per minute, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are divalent iron salt and trivalent iron salt.
500mL of the prepared rutile mother liquor is measured, 5mL (0.01M) of hexadecyl trimethyl ammonium bromide and 1500mL of ammonia water (6M) precipitator are sequentially added, the pH value of the solution is controlled to be 3.0-8.5, most of iron ions in the solution are precipitated, and the obtained precipitate is an iron oxide red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (180 ℃, 2h), filtering, washing and drying to obtain an iron oxide red product.
Example 6
As shown in figure 1, the method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (980 ℃ for 5h), naturally cooling to room temperature after calcination, reducing the oxidized industrial titanium concentrate for 4h at 900 ℃ in a hydrogen atmosphere, adding 22% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 102 ℃, condensing and refluxing, mechanically stirring for 15h at the stirring speed of 900 r/min, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are divalent iron salt and trivalent iron salt.
500mL of the prepared rutile mother liquor is measured, 5mL (0.05M) of hexadecyl trimethyl ammonium bromide and 2000mL of sodium hydroxide (2M) precipitator are sequentially added, the pH value of the solution is controlled to be 3.0-8.5, most of iron ions in the solution are precipitated, and the obtained precipitate is an iron oxide red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (at 150 ℃ for 3h), filtering, washing and drying to obtain an iron oxide red product.
Example 7
As shown in figure 1, the method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (980 ℃ for 5h), naturally cooling to room temperature after calcination, reducing the oxidized industrial titanium concentrate for 4h at 900 ℃ in a hydrogen atmosphere, adding 22% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 102 ℃, condensing and refluxing, mechanically stirring for 15h at the stirring speed of 900 r/min, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are divalent iron salt and trivalent iron salt.
500mL of the prepared rutile mother liquor is measured, 5mL (0.05M) of hexadecyl trimethyl ammonium bromide and 2000mL of sodium hydroxide (2M) precipitator are sequentially added, the pH value of the solution is controlled to be 3.0-8.5, most of iron ions in the solution are precipitated, and the obtained precipitate is an iron oxide red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (220 ℃, 1h), filtering, washing and drying to obtain an iron oxide red product.
Example 8
Referring to figure 1, a method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (950 ℃ for 6 hours), naturally cooling to room temperature after calcination, reducing the oxidized industrial titanium concentrate for 4 hours at 950 ℃ in a hydrogen atmosphere, adding 25% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 105 ℃, condensing and refluxing, mechanically stirring for 10 hours at the stirring speed of 1000 r/min, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are divalent iron salt and trivalent iron salt.
500mL of the prepared rutile mother liquor is measured, 5mL (0.1M) of sodium dodecyl benzene sulfonate and 4000mL (1M) of sodium bicarbonate precipitant are sequentially added, the pH value of the solution is controlled to be 3.0-8.5, most of iron ions in the solution are precipitated, and the obtained precipitate is an iron oxide red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (at 150 ℃ for 3h), filtering, washing and drying to obtain an iron oxide red product.
Example 9
Referring to figure 1, a method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (1000 ℃, 5 hours), naturally cooling to room temperature after calcining, reducing the oxidized industrial titanium concentrate for 4 hours at 900 ℃ in a hydrogen atmosphere, adding 22% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 100 ℃, condensing and refluxing, mechanically stirring for 18 hours at a stirring speed of 950 revolutions per minute, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are bivalent iron salt and trivalent iron salt.
Weighing 500mL of the rutile mother liquor prepared above, sequentially adding 2mL (0.06M) of sodium dodecyl benzene sulfonate, 3mL (0.06M) of polyethylene glycol, and 1000mL of sodium carbonate (5M) and 1500mL of sodium bicarbonate (5M) precipitant, controlling the pH value of the solution between 3.0 and 8.5 until most of iron ions in the solution precipitate, and obtaining the precipitate which is an iron oxide red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (at 150 ℃ for 3h), filtering, washing and drying to obtain an iron oxide red product.
Example 10
Referring to figure 1, a method for preparing series of nano Fe with high added value by taking industrial rutile mother liquor as a raw material in a mesoscale manner2O3The method of the iron oxide red comprises the following specific processes:
calcining 200g of industrial titanium concentrate in a muffle furnace (1000 ℃, 5 hours), naturally cooling to room temperature after calcining, reducing the oxidized industrial titanium concentrate for 4 hours at 900 ℃ in a hydrogen atmosphere, adding 22% of dilute hydrochloric acid into the oxidized-reduced modified titanium concentrate, wherein the mass ratio of the titanium concentrate to the dilute hydrochloric acid is 1:5, heating the mixed solution to 100 ℃, condensing and refluxing, mechanically stirring for 18 hours at a stirring speed of 950 revolutions per minute, cooling to room temperature after the reaction is finished, and filtering, standing and filtering the obtained solution to obtain a rutile mother solution, wherein the main components of the rutile mother solution are bivalent iron salt and trivalent iron salt.
500mL of the rutile mother liquor prepared above is measured, 5mL (0.08M) of triblock copolymer F127, 1000mL of sodium hydroxide (5M) and 1000mL of ammonia water (5M) precipitant are sequentially added, the pH value of the solution is controlled to be 3.0-8.5, most of iron ions in the solution are precipitated, and the obtained precipitate is an iron red precursor. And transferring the obtained iron oxide red precursor into a hydrothermal reactor, carrying out hydrothermal reaction (at 150 ℃ for 3h), filtering, washing and drying to obtain an iron oxide red product.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (1)
1. The method for preparing the nano ferric oxide iron oxide red by taking the rutile mother liquor as the raw material is characterized by comprising the following steps:
(1): taking rutile mother liquor, and sequentially adding a dispersing agent and a precipitating agent into the rutile mother liquor to obtain a precipitate iron oxide red precursor;
(2): transferring the iron oxide red precursor in the step (1) into a hydrothermal reactor, carrying out hydrothermal reaction, filtering, washing and drying to obtain a nano iron oxide red product;
in the step (1), the dispersant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, triblock copolymer F127 and polyethylene glycol;
the precipitant is one or more of ammonia water, sodium carbonate, sodium bicarbonate and sodium hydroxide;
in the step (1), the concentration of the precipitator is 1-10M, and the addition amount of the precipitator meets the following requirements: the volume ratio of the rutile mother liquor to the precipitator is 1: 3-8;
the concentration of the dispersant is 0.01-0.1M, and the addition amount of the dispersant satisfies the following conditions: the volume ratio of the rutile mother liquor to the dispersant is 100: 1;
in the step (1), the pH value of the solution is controlled to be 3.0-8.5;
in the step (1), the rutile mother liquor is prepared by the following method:
(A) the method comprises the following steps Calcining the industrial titanium concentrate, cooling to room temperature, then placing the industrial titanium concentrate in a reducing gas atmosphere for reduction, and after the reaction is finished, isolating air and cooling to room temperature to obtain oxidation/reduction modified titanium concentrate;
(B) the method comprises the following steps Adding the titanium concentrate subjected to oxidation/reduction modification in the step (A) into dilute hydrochloric acid, heating, controlling condensation reflux and stirring for reaction, cooling to room temperature after the reaction is finished, and filtering the obtained solution to obtain rutile mother liquor;
in the step (A), the calcining process conditions are as follows: calcining at 950-1050 deg.C for 4-6 h;
the reduction process conditions are as follows: reducing for 4h at 850-950 ℃;
in the step (B), the dilute hydrochloric acid is 20-25% of dilute hydrochloric acid, and the mass ratio of the oxidation/reduction modified titanium concentrate to the dilute hydrochloric acid is 1: 5;
in the step (B), the specific conditions of heating and stirring reaction are as follows: stirring for 10-24h at the temperature of 95-105 ℃ and the stirring speed of 800-1000 rpm;
the reducing gas is hydrogen, the introduction amount of the reducing gas is 5.5g per batch of industrial titanium concentrate, and the introduction amount of the reducing gas is 60g per batch of industrial titanium concentrate;
the conditions of the hydrothermal reaction in the step (2) are as follows: the temperature is 150-220 ℃, and the time is 1-3 h.
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