CN103145194A - Method of preparing iron oxide yellow by using titanium dioxide by-product - Google Patents
Method of preparing iron oxide yellow by using titanium dioxide by-product Download PDFInfo
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- CN103145194A CN103145194A CN2011104013666A CN201110401366A CN103145194A CN 103145194 A CN103145194 A CN 103145194A CN 2011104013666 A CN2011104013666 A CN 2011104013666A CN 201110401366 A CN201110401366 A CN 201110401366A CN 103145194 A CN103145194 A CN 103145194A
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Abstract
The invention provides a method of preparing iron oxide yellow by using a titanium dioxide by-product ferrous sulphate, belonging to a field of chemistry. The method comprises refining of ferrous sulphate, neutralization reaction, seed preparation, and oxidation synthesis; and the method controls a pH value of a solution during refining of the ferrous sulphate, and thus effectively removes impurities such as manganese, magnesium and zinc. In addition, by separating a seed preparation process into a neutralization reaction process and a seed preparation process, a preparation process of Fe(OH)2 suspension and an oxidation process are separated, thereby effectively controlling the seed to be spindle-shaped or needle-shaped, and improving dispersibility of the seed. The method is good in impurity removal effects, and can effectively control the seed to be spindle-shaped or needle-shaped and improve dispersibility of the seed; and the prepared iron oxide yellow has advantages of good color and high tinting strength.
Description
Technical field
The present invention relates to a kind of method that byproduct ferrous sulfate of titanium dioxide prepares ferric oxide yellow pigment, belong to the preparation method field of pigment.
Background technology
Titanium white is a kind of white inorganic pigment of high-grade high-quality, mainly contains two kinds of crystal formations of anatase titanium dioxide and rutile-type.Because its density, specific inductivity and specific refractory power are all very superior, be considered to the best a kind of white pigment of performance in the world, be widely used in the industry such as coating, plastics, papermaking, printing, printing ink and rubber.At present, the production method of titanium dioxide has two kinds of sulfuric acid process and chlorination processs, because Production By Sulfuric Acid Process technique is relatively simple, and can produce with the lower ilmenite concentrate of taste, and China is mainly Titanium White Production By Sulfuric Acid Process at present, and its ratio accounts for 98%.
3.5～4 tons of ferrous sulfate of the about by-product of 1 ton of titanium white of the every product of Titanium White Production By Sulfuric Acid Process.Titanium white output in 2010 reaches 160～1,800,000 tons according to statistics, and useless by-product ferrous sulfate during (hereinafter referred to as ferrous sulfate as side product) output is up to 640～7,200,000 tons.So a large amount of ferrous sulfate as side product are as still adopted original accumulation mode, and shared place is big and the impact of environment has all seriously been restricted to the development of titanium dioxide industry.
For ferrous sulfate as side product is recycled fully, also had in the past the people by the titanium white ferrous sulfate as side product for doing iron catalyst, water purification agent, fodder additives, soil improvement agent etc., the amount of the titanium white ferrous sulfate as side product of relative output, these consumptions of processing approach are all very little, still have a large amount of ferrous sulfate as side product urgently to fully utilize, not so will cause serious environmental pollution, and waste precious resources.And utilize the titanium white ferrous sulfate as side product to prepare iron oxide pigment, it is the better approach that fully utilizes, turns waste into wealth.
China produces iron oxide yellow take " liquid and solid phase reaction " method as main, and main raw material is enamel plant's scrap iron (scrap stock), data presentation, and one ton of iron oxide yellow of every production just needs 900 kilograms of left and right low-carbon (LC) sheet irons.At present, the iron sheet price increase, source of goods shortage, in order to reduce costs, to find so new raw material sources just very necessary.And utilize the titanium white ferrous sulfate as side product to prepare ferric oxide yellow pigment, can consume in a large number ferrous sulfate as side product, iron oxide pigment approximately per ton can consume 4 tons of ferrous sulfate as side product, solved the problem that the ferrous sulfate as side product that produces in the Producing Titanium Dioxide process is hoarded environmental pollution in a large number, can reduce the ferric oxide yellow pigment production cost again, realize the comprehensive utilization of resource.
At present, in prior art, the method for utilizing the titanium white ferrous sulfate as side product to prepare ferric oxide yellow pigment has been arranged.Disclose such as Chinese patent ZL02148429C a kind of method that titanium white ferrous sulfate as side product is produced ferric oxide yellow pigment, the method specifically comprises the steps:
(1) ferrous sulfate is refining, at first dissolve the titanium white ferrous sulfate as side product, take the sulfuric acid adjust pH as 1.0～1.5, add a certain amount of iron sheet, control temperature at 50～70 ℃, being hydrolyzed 6～10h, to reach the pH value be 3.0～4.5, being diluted to iron vitriol concentration is 350～450g/L, add flocculation agent, stirring, standing sedimentation 4～6h, supernatant liquid is the POV ferrous iron solution; (2) crystal seed preparation, in traditional seed tank, ferrous (initial pH value is 6.0～8.0) solution of ammonia and above-mentioned POV, at 10～40 ℃, with air reaction, through 18～36h, system pH reaches 5.0～7.0, and makes needle-like oyster ferric oxide crystal seed; (3) oxidizing reaction, in the conventional oxidation bucket, add above-mentioned crystal seed, be warming up to 60～95 ℃, constant temperature, adjust pH to 2.0～5.0, add continuously above-mentioned refining copperas solution, air and ammonia, maintenance system pH value is 2.0～5.0, and iron vitriol concentration is at 10～45g/L, oxidation 40～130h, make the iron oxide yellow slurry; (4) filtration, washing, oven dry, pulverizing, packing make the finished product ferric oxide yellow pigment.
In above-mentioned technology, in the treating process to ferrous sulfate, the conditions such as the pH value by controlling solution and temperature, can effectively remove the impurity titanium in ferrous sulfate; Because the deposition condition of magnesium, zinc, mn ion must be greater than 7, so at above-mentioned pH value condition is next in can't removing ferrous sulfate impurity magnesium, zinc and manganese, and the existence of magnesium, zine ion can cause the color of iron oxide yellow product partially white, the existence of mn ion can cause the color of iron oxide yellow product partially black, product ferric oxide yellow is caused to direct impact, and color is the important indicator of iron oxide yellow product.If the pH value is adjusted to and is greater than 7, can make Fe simultaneously
2+precipitate, affect the productive rate of subsequent oxidation iron oxide yellow.
In addition, in above-mentioned technology, to ferrous sulfate carry out impurity elimination refining after, in the ferrous sulfate after making with extra care, add ammoniacal liquor directly to generate the ferric oxide crystal seed through single step reaction under the blowing air condition, in above-mentioned reaction process, at first ferrous sulfate and ammoniacal liquor react and generate Fe (OH)
2suspensoid, the existence of air makes this part product be oxidised with air to immediately alpha-feooh (being hydrous iron oxide) when generating, when alpha-feooh reaches the minimum supersaturation concentration of nucleation requirement, nucleus nucleation in solution, once nucleus forms, at first the alpha-feooh then generated can make the nucleus formed grow up rapidly, and the new nucleus of difficult generation, the alpha-feooh crystal seed that this mode easily causes reaction to generate is few, established crystal seed growth rate is too fast, shape is wayward, generation is shaped as the master with needle-like or fusiformis crystal seed, and mix the product that cylindrical crystal seed is arranged, wherein cylindrical crystal seed is iron oxide red, and the existence of this part cylindrical crystal seed makes the transmittance of alpha-feooh, absorb light rate and refracted light rate have been subject to impact, thereby directly cause the ferric oxide yellow of generation partially dark.
Summary of the invention
First technical problem to be solved by this invention be in prior art after ferrous sulfate is made with extra care, add ammoniacal liquor in the ferrous sulfate after refining, directly generate the ferric oxide crystal seed through single step reaction under the blowing air condition, cause the crystal seed that generates in reaction process few and can not effectively control the nucleation of crystal seed and the growth of nucleus, causing in crystal seed to mix has cylindrical crystal seed, makes the finished product ferric oxide yellow prepared be subject to direct impact.
Second technical problem to be solved by this invention is that the pH value condition while in prior art, ferrous sulfate being made with extra care can't be removed impurity magnesium, zinc and the manganese in ferrous sulfate, the existence of magnesium, zine ion causes direct impact to product ferric oxide yellow, if the pH value is adjusted to and is greater than 7, can make Fe simultaneously
2+precipitate, affect the productive rate of subsequent oxidation iron oxide yellow.
In order to solve the problems of the technologies described above, the invention provides a kind of method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow, comprise the steps:
(1) ferrous sulfate is refining
Utilize byproduct ferrous sulfate of titanium dioxide preparation iron vitriol solution, the pH value of regulating this solution is 1～2.5, byproduct ferrous sulfate of titanium dioxide is carried out to the hydrolysis treatment of titanium;
Add iron powder or iron sheet in the iron vitriol solution after the titanium hydrolysis treatment, to the Fe in solution
3+reducing and processing the also pH value of regulator solution is 6.0～6.5, byproduct ferrous sulfate of titanium dioxide is carried out to the precipitation process of magnesium, manganese, zinc;
Add flocculation agent in the solution after titanium hydrolysis treatment and magnesium, manganese, zinc precipitation process, stir, filter after standing sedimentation, filtrate is the copperas solution after refining;
(2) Fe (OH)
2generation
Add alkaline solution in described copperas solution after refining, carry out neutralization reaction under 10～39 ℃, hierarchy of control pH value is 6.0～7.5, and the white precipitate of the generation in solution becomes neutralization reaction end when blackish green;
(3) iron oxide yellow crystal seed preparation
Reacted system solution in step (2) is diluted, pass into wherein air and reacted, until system pH, reached at 3～4 o'clock, made needle-like oyster iron oxide yellow crystal seed;
(4) oxidation is synthetic
The iron oxide yellow crystal seed prepared in step (3) is diluted, slowly be warming up to 75～85 ℃, pass into wherein air, the control air capacity is 2～5 times of the air capacity that passes in step (3), maintenance system pH value is 2～3.5, and oxidation obtains the iron oxide yellow slurries more than 40 hours;
(5) aftertreatment
Iron oxide yellow slurries after step (4) is processed are filtered, are washed, are dried the iron oxide yellow that gets product successively.
In described step (1), under 10～80 ℃, the described iron vitriol strength of solution of preparation is 350～490g/L.
In described step (1), the pH value of regulating iron vitriol solution with sulfuric acid is 2.
In described step (1), the add-on of described flocculation agent is 0.05% of iron vitriol quality.
In described step (1), before adding flocculation agent, the solution after titanium hydrolysis treatment and magnesium, manganese, zinc precipitation process is lowered the temperature, reduce to room temperature to system temperature.
In step (1), the time of standing sedimentation is 1～2h.
In step (2), hierarchy of control pH value is 6.5～7.2.
The mass ratio of described alkaline solution and iron vitriol is 0.05～0.09.
In described step (3), reacted system solution in step (2) is diluted to 200～300g/L.
In described step (3), after 2.5～11 hours, system pH reaches 3～4.
In described step (3), be warming up to 75～85 ℃ in 4～8 hours.
In described step (3), it is 1/40～1/10 of reactor volume that per minute passes into described air capacity.
In described step (4), to the dilution after solution in add excessive iron sheet, maintenance system pH value is 2～3.5.
In described step (4), the iron oxide yellow crystal seed prepared in step (3) is diluted to 100～150g/L.
The method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of the present invention, at first need to utilize byproduct ferrous sulfate of titanium dioxide preparation iron vitriol solution, and control pH value is 1～2.5, make titanium impurity in iron vitriol solution in this pH value Water Under solution, generate the Ti that can be changed into the rapid sedimentation of floss and decomposition by adding after flocculation agent
2oH
2o; When the iron vitriol solution preparation, preferably preparation under 50～80 ℃, be to have guaranteed the dissolved efficiency of byproduct ferrous sulfate of titanium dioxide when considering stability of solution; In order to remove the Fe in byproduct ferrous sulfate of titanium dioxide
3+, in the iron vitriol solution after processing except titanium, add iron powder or iron sheet to Fe
3+reduced, removed Fe
3+; Further, in order to improve the purity of the ferrous sulfate prepared, in method of the present invention, by the interpolation of iron powder or iron sheet, and to regulate the pH value be 6.0～6.5, thereby realized the precipitate reduction to the magnesium in iron vitriol solution, manganese, zine ion.Add flocculation agent in the solution carried out after above-mentioned processing, thereby fully realize titanyl hydrate, the precipitation of magnesium, manganese, zinc removes, be convenient to it is carried out effectively filtering the copperas solution after being made with extra care.
Then, in the copperas solution after refining, add alkaline solution, hierarchy of control pH value is 6.0～7.5, carries out neutralization reaction under 10～39 ℃, thus generation Fe (OH)
2precipitation, precipitation to be generated transfers neutralization reaction when blackish green to by white and finishes; In above-mentioned neutralization reaction, guarantee Fe
2+react fully, at first Fe
2+reaction generates white Fe (OH)
2precipitation, still, due to Fe (OH)
2unstable, newly-generated Fe (OH)
2be dissolved into very soon a small amount of dioxygen oxidation in solution in air, be converted into the intermediate product of ironic hydroxide, i.e. the flocks of some greyish-green, in ie in solution, white precipitate changes into when blackish green, show that neutralization reaction finishes, should finish immediately reaction and avoid Fe (OH)
2be further oxided.But, generally speaking, in the neutralization reaction process, mainly still generate a large amount of Fe (OH)
2suspensoid, Fe (OH)
2seldom, concentration not yet reaches the minimum supersaturation concentration that nucleation requires to the oxidized alpha-feooh obtained of suspensoid, now not nucleus generation in solution.
Because the ferrous hydroxide prepared after this neutralization reaction is precipitated as flocculent substance, so it is dense, if directly pass into wherein air, air can't carry out contact reacts fully with the ferrous hydroxide precipitation, so when preparing the iron oxide yellow crystal seed, need first to be diluted the system solution after neutralization reaction, then pass into wherein air and reacted, reach at 3～4 o'clock until system pH, make needle-like oyster iron oxide yellow crystal seed; In this preparation process, pass into air in the solution after neutralization reaction, owing to now in solution, containing Fe (OH)
2suspensoid, after passing into enough air, airborne oxygen can Oxidation of Fe (OH)
2, generate alpha-feooh.In addition, owing to having contained a large amount of Fe (OH) in solution
2so now oxidation obtains the speed of alpha-feooh can be very fast, after the concentration of the solute alpha-feooh in solution meets and exceeds the one-tenth nuclear concentration of crystal seed, nucleus will form fast and be evenly distributed.In above-mentioned two-step reaction, first the copperas solution after refining is carried out to simple neutralization reaction, and do not pass into air when neutralization reaction, a large amount of Fe (OH) of main generation in solution
2suspensoid; After the neutralization reaction finishes, then pass into air in solution, carry out oxidation synthetic iron oxide citrine kind.
Finally, the iron oxide yellow crystal seed prepared is diluted, be warming up to 80～83 ℃, pass into wherein air, the control air capacity is 2～5 times of the air capacity that passes in step (3), maintenance system pH value is 2～3.5, and further oxidation obtains the iron oxide yellow slurries more than 40 hours, carries out the aftertreatment iron oxide yellow that gets product.In above-mentioned iron oxide yellow slurries preparation process, along with the carrying out of oxidizing reaction, H in solution
+concentration constantly increase, pH descends, amorphous substance Fe (OH)
2transform gradually Fe to crystalline state material FeOOH
2+gradually become Fe
3+, solution becomes yellow; In iron oxide yellow slurries preparation process, as the pH of solution, lower than 2 the time, FeOOH dissolves, and can have influence on the productive rate of iron oxide yellow, so, in oxidising process, control the pH value of slurries system in 2～3.5 scopes, after the oxidation enough time, obtains the iron oxide yellow slurries.
The present invention compared with prior art has following advantage:
The present invention is divided into Fe (OH) by seed crystal production process in prior art
2generative process and iron oxide yellow seed crystal production process, preparing a large amount of Fe (OH)
2after suspensoid, carry out the preparation of iron oxide yellow crystal seed passing into air, can generate and generate a large amount of iron oxide yellow crystal seeds within a short period of time, and can effectively control the nucleation of crystal seed and the growth of nucleus, and then effectively control crystal seed be shaped as fusiformis or aciculiform, and improve the dispersiveness of crystal seed.
In addition, in preparation method of the present invention by adding iron powder or iron sheet can control more accurately the pH value of ferrous sulfate solution when refining, thereby under appropriate pH value condition, realize the reduction to magnesium, manganese, zine ion by reduction reaction, thereby realize removing the purpose of impurity magnesium, manganese, zine ion, obtain the high-purity mangesium oxide iron oxide yellow.It is good that the sulfuric acid iron oxide yellow prepared by the method has form and aspect, the tinting strength advantages of higher.
The accompanying drawing explanation
The TEM characterization test picture of the iron oxide yellow prepared in Fig. 1 embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail.
embodiment 1
(1) ferrous sulfate is refining
Under normal temperature, utilize the iron vitriol solution 500ml that the byproduct ferrous sulfate of titanium dioxide compound concentration is 350g/L, the pH value of regulating this solution with sulfuric acid is 1, and byproduct ferrous sulfate of titanium dioxide is carried out to the titanium hydrolysis treatment; Add 26g iron powder reducing Fe again in the iron vitriol solution after the titanium hydrolysis treatment
3+and adjusting pH value is 6.0, magnesium, manganese, zine ion are reduced to the precipitation that obtains magnesium, manganese, zinc simple substance, add the 0.09g polyacrylamide flocculant in the solution after titanium hydrolysis treatment and magnesium, manganese, zinc precipitation process, after stirring, standing sedimentation 5h, filter, remove product after titanium hydrolysis and magnesium, manganese, zinc precipitation, filtrate is the copperas solution after refining;
(2) Fe (OH)
2generation
Get described copperas solution 375ml after refining, add wherein the NaOH solution of 9g 30wt%, carry out neutralization reaction under 10 ℃, hierarchy of control pH value is 6.0, and the white precipitate generated in solution becomes neutralization reaction end when blackish green;
(3) iron oxide yellow crystal seed preparation
It is 200g/L that reacted system solution in step (2) is diluted to concentration, passes into wherein air and is reacted, and the speed that passes into air is 60ml/min, and to pass into air capacity be 1/40 of reactor volume to per minute; Reach at 3.0 o'clock until system pH, make needle-like oyster iron oxide yellow crystal seed;
(4) oxidation is synthetic
It is 150g/L that the iron oxide yellow crystal seed prepared in step (3) is diluted to concentration, controlling the heating-up time is that 4h slowly is warming up to 75 ℃, to the dilution after solution in pass into air, the control air capacity is 2 times of the air capacity that passes in step (3), and add the iron sheet of 40g, maintenance system pH value is 3.5, and oxidation obtains the iron oxide yellow slurries more than 40 hours;
(5) aftertreatment
Iron oxide yellow slurries after step (4) is processed are filtered, are washed, are dried the iron oxide yellow that gets product successively.
After testing, the total iron amount of the finished product iron oxide yellow of preparation is with Fe
2o
3meter, content is 98%.
embodiment 2
(1) ferrous sulfate is refining
Under 50 ℃, utilize the iron vitriol solution 500ml that the byproduct ferrous sulfate of titanium dioxide compound concentration is 370g/L, the pH value of regulating this solution with sulfuric acid is 1.5, and byproduct ferrous sulfate of titanium dioxide is carried out to the titanium hydrolysis treatment; Add 28g iron powder reducing Fe again in the iron vitriol solution after the titanium hydrolysis treatment
3+and adjusting pH is 6.1, magnesium, manganese, zine ion are reduced to the precipitation that obtains magnesium, manganese, zinc simple substance, when solution is cooled to room temperature, add the 0.09g polyacrylamide flocculant in the solution after titanium hydrolysis treatment and magnesium, manganese, zinc precipitation process, after stirring, standing sedimentation 2h, filter, remove product after titanium hydrolysis and magnesium, manganese, zinc precipitation, filtrate is the copperas solution after refining;
(2) Fe (OH)
2generation
Get described copperas solution 375ml after refining, add wherein the NaOH solution of 9.5g30wt%, carry out neutralization reaction under 20 ℃, hierarchy of control pH value is 6.5, and the white precipitate generated in solution becomes neutralization reaction end when blackish green;
(3) iron oxide yellow crystal seed preparation
It is 250g/L that reacted system solution in step (2) is diluted to concentration, passes into wherein air and is reacted, and the speed that passes into air is 80ml/min, and to pass into air capacity be 1/30 of reactor volume to per minute; Reach at 3.5 o'clock until system pH, make needle-like oyster iron oxide yellow crystal seed;
(4) oxidation is synthetic
It is 130g/L that the iron oxide yellow crystal seed prepared in step (3) is diluted to concentration, controlling the heating-up time is that 8h slowly is warming up to 83 ℃, to the dilution after solution in pass into air, the control air capacity is 3 times of the air capacity that passes in step (3), and to add 42g iron sheet maintenance system pH value be 2, oxidation obtains the iron oxide yellow slurries more than 40 hours;
(5) aftertreatment
Iron oxide yellow slurries after step (4) is processed are filtered, are washed, are dried the iron oxide yellow that gets product successively.
After testing, the total iron amount of the finished product iron oxide yellow of preparation is with Fe
2o
3meter, content is 98%.
embodiment 3
(1) ferrous sulfate is refining
Under 60 ℃, utilize the iron vitriol solution 500ml that the byproduct ferrous sulfate of titanium dioxide compound concentration is 400g/L, the pH value of regulating this solution with sulfuric acid is 2.0, and byproduct ferrous sulfate of titanium dioxide is carried out to the titanium hydrolysis treatment; Add 30g iron powder reducing Fe again in the iron vitriol solution after the titanium hydrolysis treatment
3+and adjusting pH is 6.0, magnesium, manganese, zine ion are reduced to the precipitation that obtains magnesium, manganese, zinc simple substance, when solution is cooled to room temperature, add the 0.1g polyacrylamide flocculant in the solution after titanium hydrolysis treatment and magnesium, manganese, zinc precipitation process, after stirring, standing sedimentation 1.5h, filter, remove product after titanium hydrolysis and magnesium, manganese, zinc precipitation, filtrate is the copperas solution after refining;
(2) Fe (OH)
2generation
Get described copperas solution 375ml after refining, add wherein the NaOH solution of 12g 30wt%, carry out neutralization reaction under 30 ℃, hierarchy of control pH value is 7.0, and the white precipitate of the generation in solution becomes neutralization reaction end when blackish green;
(3) iron oxide yellow crystal seed preparation
It is 300g/L that reacted system solution in step (2) is diluted to concentration, passes into wherein air and is reacted, and the speed that passes into air is 100ml/min, and to pass into air capacity be 1/25 of reactor volume to per minute; Reach at 4.0 o'clock until system pH, make needle-like oyster iron oxide yellow crystal seed;
(4) oxidation is synthetic
It is 150g/L that the iron oxide yellow crystal seed prepared in step (3) is diluted to concentration, controlling the heating-up time is that 5h slowly is warming up to 80 ℃, to the dilution after solution in pass into air, the control air capacity is 3 times of the air capacity that passes in step (3), and to add 45g iron powder maintenance system pH value be 2.5, oxidation obtains the iron oxide yellow slurries more than 40 hours;
(5) aftertreatment
Iron oxide yellow slurries after step (4) is processed are filtered, are washed, are dried the iron oxide yellow that gets product successively.
After testing, the total iron amount of the finished product iron oxide yellow of preparation is with Fe
2o
3meter, content is 99%.
embodiment 4
(1) ferrous sulfate is refining
Under 70 ℃, utilize the iron vitriol solution 500ml that the byproduct ferrous sulfate of titanium dioxide compound concentration is 490g/L, the pH value of regulating this solution with hydrochloric acid is 2.5, and byproduct ferrous sulfate of titanium dioxide is carried out to the titanium hydrolysis treatment; Add 36g iron powder reducing Fe again in the iron vitriol solution after the titanium hydrolysis treatment
3+and adjusting pH is 6.3, magnesium, manganese, zine ion are reduced to the precipitation that obtains magnesium, manganese, zinc simple substance, when solution is cooled to room temperature, add the 0.12g polyacrylamide flocculant in the solution after titanium hydrolysis treatment and magnesium, manganese, zinc precipitation process, after stirring, standing sedimentation 1h, filter, remove product after titanium hydrolysis and magnesium, manganese, zinc precipitation, filtrate is the copperas solution after refining;
(2) Fe (OH)
2generation
Get described copperas solution 375ml after refining, add wherein the NaOH solution of 16g30wt%, carry out neutralization reaction under 39 ℃, hierarchy of control pH value is 7.2, and the white precipitate of the generation in solution becomes neutralization reaction end when blackish green;
(3) iron oxide yellow crystal seed preparation
It is 300g/L that reacted system solution in step (2) is diluted to concentration, passes into wherein air and is reacted, and the speed that passes into air is 150ml/min, and to pass into air capacity be 1/20 of reactor volume to per minute; Reach at 3.5 o'clock until system pH, make needle-like oyster iron oxide yellow crystal seed;
(4) oxidation is synthetic
It is 100g/L that the iron oxide yellow crystal seed prepared in step (3) is diluted to concentration, be warming up to 81 ℃, pass into wherein air, the control air capacity is 5 times of the air capacity that passes in step (3), and to add 55g iron sheet maintenance system pH value be 3.5, oxidation obtains the iron oxide yellow slurries more than 40 hours;
(5) aftertreatment
Iron oxide yellow slurries after step (4) is processed are filtered, are washed, are dried the iron oxide yellow that gets product successively.
After testing, the total iron amount of the finished product iron oxide yellow of preparation is with Fe
2o
3meter, content is 98%.
embodiment 5
(1) ferrous sulfate is refining
Under 80 ℃, utilize the iron vitriol solution 500ml that the byproduct ferrous sulfate of titanium dioxide compound concentration is 400g/L, the pH value of regulating this solution with sulfuric acid is 2.0, and byproduct ferrous sulfate of titanium dioxide is carried out to the titanium hydrolysis treatment; Add 30g iron sheet reduction Fe again in the iron vitriol solution after the titanium hydrolysis treatment
3+and adjusting pH is 6.5, magnesium, manganese, zine ion are reduced to the precipitation that obtains magnesium, manganese, zinc simple substance, when solution is cooled to room temperature, add the 0.1g polyacrylamide flocculant in the solution after titanium hydrolysis treatment and magnesium, manganese, zinc precipitation process, after stirring, standing sedimentation 1.0h, filter, remove product after titanium hydrolysis and magnesium, manganese, zinc precipitation, filtrate is the copperas solution after refining;
(2) Fe (OH)
2generation
Get described copperas solution 375ml after refining, add wherein the NaOH solution of 12g30wt%, carry out neutralization reaction under 30 ℃, hierarchy of control pH value is 7.5, and the white precipitate of the generation in solution becomes neutralization reaction end when blackish green;
(3) iron oxide yellow crystal seed preparation
It is 300g/L that reacted system solution in step (2) is diluted to concentration, passes into wherein air and is reacted, and the speed that passes into air is 100ml/min, and to pass into air capacity be 1/10 of reactor volume to per minute; Reach at 4.0 o'clock until system pH, make needle-like oyster iron oxide yellow crystal seed;
(4) oxidation is synthetic
It is 100g/L that the iron oxide yellow crystal seed prepared in step (3) is diluted to concentration, controlling the heating-up time is that 5h slowly is warming up to 85 ℃, to the dilution after solution in pass into air, the control air capacity is 3 times of the air capacity that passes in step (3), and to add 45g iron powder maintenance system pH value be 2.5, oxidation obtains the iron oxide yellow slurries more than 40 hours;
(5) aftertreatment
Iron oxide yellow slurries after step (4) is processed are filtered, are washed, are dried the iron oxide yellow that gets product successively.
After testing, the total iron amount of the finished product iron oxide yellow of preparation is with Fe
2o
3meter, content is 97%.
The total iron amount of the finished product iron oxide yellow prepared in above-described embodiment is with Fe
2o
3meter, content is all 96～99%, and maximum can reach 99%.
Produce the detection method of iron oxide yellow in particle-size analyzer and GB/T1863-2008 obtained in above-described embodiment and carry out the detections such as form and aspect, meet the iron oxide pigment national standard of GB/T1863-2008.
experimental example
The present invention has also carried out the TEM characterization test to the iron oxide yellow prepared in above-described embodiment 1, and as shown in Figure 1, as we can see from the figure, the crystalline form of the iron oxide yellow of generation is fusiformis and aciculiform to the test picture, does not exist cylindrical.
Obviously, above-described embodiment is only for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments, and the apparent variation of being extended out thus or change are still among the protection domain in the invention claim.
Claims (14)
1. a method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow, comprise the steps:
(1) ferrous sulfate is refining
Utilize byproduct ferrous sulfate of titanium dioxide preparation iron vitriol solution, the pH value of regulating this solution is 1～2.5, byproduct ferrous sulfate of titanium dioxide is carried out to the hydrolysis treatment of titanium;
Add iron powder or iron sheet in the iron vitriol solution after the titanium hydrolysis treatment, to the Fe in solution
3+reducing and processing the also pH value of regulator solution is 6.0～6.5, byproduct ferrous sulfate of titanium dioxide is carried out to the precipitation process of magnesium, manganese, zinc;
To through the titanium hydrolysis treatment and, add flocculation agent in solution after magnesium, manganese, zinc precipitation process, stir, filter after standing sedimentation, filtrate is the copperas solution after refining;
(2) Fe (OH)
2generation
Add alkaline solution in described copperas solution after refining, carry out neutralization reaction under 10～39 ℃, hierarchy of control pH value is 6.0～7.5, and the white precipitate of the generation in solution becomes neutralization reaction end when blackish green;
(3) iron oxide yellow crystal seed preparation
Reacted system solution in step (2) is diluted, pass into wherein air and reacted, until system pH, reached at 3～4 o'clock, made needle-like oyster iron oxide yellow crystal seed;
(4) oxidation is synthetic
The iron oxide yellow crystal seed prepared in step (3) is diluted, slowly be warming up to 75～85 ℃, pass into wherein air, the control air capacity is 2～5 times of the air capacity that passes in step (3), maintenance system pH value is 2～3.5, and oxidation obtains the iron oxide yellow slurries more than 40 hours;
(5) aftertreatment
Iron oxide yellow slurries after step (4) is processed are filtered, are washed, are dried the iron oxide yellow that gets product successively.
2. the method for utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow according to claim 1, is characterized in that, in described step (1), under 10～80 ℃, the described iron vitriol strength of solution of preparation is 350～490g/L.
3. the method for utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow according to claim 1 and 2, is characterized in that, in described step (1), the pH value of regulating iron vitriol solution with sulfuric acid is 2.
4. according to claim 1 or the 2 or 3 described methods of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow, it is characterized in that, in described step (1), the add-on of described flocculation agent is 0.05% of iron vitriol quality.
5. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-4, it is characterized in that, in described step (1), before adding flocculation agent, solution after titanium hydrolysis treatment and magnesium, manganese, zinc precipitation process is lowered the temperature, reduced to room temperature to system temperature.
6. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-5, it is characterized in that, in step (1), the time of standing sedimentation is 1～2h.
7. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-6, it is characterized in that, in step (2), hierarchy of control pH value is 6.5～7.2.
8. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-7, it is characterized in that, the mass ratio of described alkaline solution and iron vitriol is 0.05～0.09.
9. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-8, it is characterized in that, in described step (3), reacted system solution in step (2) is diluted to 200～300g/L.
10. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-9, it is characterized in that, in described step (3), after 2.5～11 hours, system pH reaches 3～4.
11. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-10, it is characterized in that, in described step (3), be warming up to 75～85 ℃ in 4～8 hours.
12. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-11, it is characterized in that, in described step (3), it is 1/40～1/10 of reactor volume that per minute passes into described air capacity.
13. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-12, it is characterized in that, in described step (4), to the dilution after solution in add excessive iron sheet, maintenance system pH value is 2～3.5.
14. according to the arbitrary described method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow of claim 1-13, it is characterized in that, in described step (4), the iron oxide yellow crystal seed prepared in step (3) is diluted to 100～150g/L.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502512A (en) * | 2016-02-04 | 2016-04-20 | 天津大学 | Method for preparing iron oxide yellow from steel pickling wastewater |
| CN107352585A (en) * | 2017-08-02 | 2017-11-17 | 浙江神光材料科技有限公司 | The preparation method of transparent zinc-iron yellow pigment |
| CN108455681A (en) * | 2018-02-05 | 2018-08-28 | 吉林建筑大学 | A method of preparing iron oxide yellow using iron content, aluminum i ndustry waste water |
| CN113061730A (en) * | 2021-03-23 | 2021-07-02 | 北京佰利格瑞资源科技有限公司 | Method for removing iron in waste ternary lithium battery recovery process |
| CN113104901A (en) * | 2021-04-13 | 2021-07-13 | 江西理工大学 | Method for preparing iron oxide yellow from rare earth waste acid leaching residues |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104999A (en) * | 1994-06-01 | 1995-07-12 | 山西省阳泉市磁粉工程筹建处 | Purified technology for ferrous sulfate of titanium white powder by-product |
| 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 |
| RU2366674C2 (en) * | 2007-08-31 | 2009-09-10 | Юрий Михайлович Хамидулин | Method for preparation of iron oxide pigment from specularite |
| 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 |
-
2011
- 2011-12-06 CN CN201110401366.6A patent/CN103145194B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104999A (en) * | 1994-06-01 | 1995-07-12 | 山西省阳泉市磁粉工程筹建处 | Purified technology for ferrous sulfate of titanium white powder by-product |
| 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 |
| RU2366674C2 (en) * | 2007-08-31 | 2009-09-10 | Юрий Михайлович Хамидулин | Method for preparation of iron oxide pigment from specularite |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 张桂香等: "《大学化学实验——无机及分析化学实验分册》", 28 February 2011, 天津大学出版社 * |
| 邵建华等: ""钛白副产硫酸亚铁生产氧化铁黄的研究"", 《化学世界》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502512A (en) * | 2016-02-04 | 2016-04-20 | 天津大学 | Method for preparing iron oxide yellow from steel pickling wastewater |
| CN107352585A (en) * | 2017-08-02 | 2017-11-17 | 浙江神光材料科技有限公司 | The preparation method of transparent zinc-iron yellow pigment |
| CN108455681A (en) * | 2018-02-05 | 2018-08-28 | 吉林建筑大学 | A method of preparing iron oxide yellow using iron content, aluminum i ndustry waste water |
| CN113061730A (en) * | 2021-03-23 | 2021-07-02 | 北京佰利格瑞资源科技有限公司 | Method for removing iron in waste ternary lithium battery recovery process |
| CN113104901A (en) * | 2021-04-13 | 2021-07-13 | 江西理工大学 | Method for preparing iron oxide yellow from rare earth waste acid leaching residues |
| CN113104901B (en) * | 2021-04-13 | 2024-02-09 | 江西理工大学 | Method for preparing iron oxide yellow from rare earth waste acid leaching slag |
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