CN100357361C - 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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- CN100357361C CN100357361C CNB2005100366485A CN200510036648A CN100357361C CN 100357361 C CN100357361 C CN 100357361C CN B2005100366485 A CNB2005100366485 A CN B2005100366485A CN 200510036648 A CN200510036648 A CN 200510036648A CN 100357361 C CN100357361 C CN 100357361C
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Abstract
The present invention relates to a method for preparing high purity iron oxide yellow and iron oxide red by utilizing titanium pigment by-product ferrisulphas, which comprises the following procedures: in condition that the temperature is under 60 DGE C, carrying out fine purification and subtraction with the solution of the by-product ferrisulphas of titanium pigment; in condition of existing oxidizing agents, adjusting the pH value of the solution to reach the goal of removing titanium by hydrolyzation and removing metal ions such as zinc, manganese, etc. by coprecipitation; then, controlling the pH value of the solution and oxidizing the product by ventilating the product in condition of normal temperature; obtaining iron oxide yellow and iron oxide red in different conditions with the purity of 99.5%. The present invention has the advantages of simple preparing process, low cost and high purity of product, and is suitable for a comprehensive utilization of the by-product ferrisulphas of titanium pigment.
Description
[technical field]
The present invention relates to the preparation method of a kind of iron oxide yellow and red iron oxide, especially relate to a kind of method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare iron oxide yellow and red iron oxide.
[background technology]
Iron oxide yellow and red iron oxide are a kind of common mineral dyes, are widely used in fields such as coating, building materials, plastics, electronics; High-purity red iron oxide can be used as the rumbling compound of opticglass, senior abrasive substance.The common production method of iron oxide yellow and red iron oxide mainly contains following three kinds:
First kind of preparation method is the green vitriol calcination method: this method is to be that raw material carries out high-temperature calcination with pure green vitriol, the red iron oxide of generation through washing, dry, be crushed into product.
Second kind of preparation method is the wet method air oxidation process: the main raw material of this method is an iron sheet, the technological process of producing is from the preparation crystal seed, adopt sulfuric acid or nitric acid to prepare crystal seed, crystal seed is added in the second oxidation bucket, add iron sheet and water, adding ferrous salt again is reaction medium, and steam is warmed up to more than 70 ℃, under certain pH value condition, blast atmospheric oxidation, obtain iron oxide yellow and red iron oxide.
The third preparation method is an aniline process: this method is to use iron reduction oil of mirbane, produces iron oxide yellow when producing aniline.
The main raw material of the wet type method for producing of above-mentioned iron oxide yellow and red iron oxide all is iron sheet and sulfuric acid, and raw material route has limited the production of iron oxide yellow and red iron oxide to a certain extent; Simultaneously, in the sulfuric acid method titanium pigment industrial production, produce a large amount of by-product ferrous sulfate durings, and by-product ferrous sulfate during is fully utilized not, becomes the burden that sulfuric acid method titanium pigment is produced.
Produce iron oxide yellow and red iron oxide with by-product ferrous sulfate during production of titanium white powder, the more domestic report that documents and patent are arranged, for example Chinese patent application number is 02148428.7 to disclose the method that a kind of titanium white ferrous sulfate as side product is produced ferric oxide red colorant, and Chinese patent application number is 02148429.5 to disclose the method that a kind of titanium white ferrous sulfate as side product is produced ferric oxide yellow pigment, above-mentioned two patents are temperature (50～70 ℃) iron sheet reduction control hydrolysis 6～10 hours in adopting, flocculation, settlement separate, refining iron vitriol, the ammonia neutralization makes crystalloid red iron oxide crystal seed; Adopt ammoniacal liquor neutralization, synthetic red iron oxide or the ferric oxide yellow pigment of making of atmospheric oxidation.
The main difference of comprehensive various document and the described production technique of patent concentrates on the refining and oxidation of copperas solution, and other unit operation such as rinsing or washing, filtering separation, oven dry, calcining all belong to the Chemical Manufacture common operation, and difference is not remarkable.At present, the technology of utilizing by-product of white titanium pigment to produce iron oxide yellow and red iron oxide comprises:
The purification of copperas solution: copperas solution is heated to 70 ℃～95 ℃, and transferring the pH value of solution with sulfuric acid is 1～3.5, utilize in the iron sheet with acidity, ferric iron is reduced into ferrous, the copperas solution that is purified; It is ferrous perhaps to obtain bright sulfur acid with the mode of recrystallization, and dissolving obtains copperas solution then.
Second oxidation: under certain conditions, bubbling air prepares crystal seed, and crystal seed is added the copperas solution that purifies, and is heated to more than 70 ℃, and under certain pH condition, bubbling air makes the ferrous sulfate oxidation again, obtains iron oxide yellow and red iron oxide; Rinsing then, filtering separation, oven dry, calcining obtain iron oxide yellow and red iron oxide.
The existing the whole bag of tricks that utilizes by-product ferrous sulfate during production of titanium white powder to produce iron oxide yellow and red iron oxide, ubiquitous problem is: the one, in purifying (making with extra care), oxidising process, all need copperas solution is heated to 60 ℃～95 ℃, consume a large amount of energy; The 2nd, in (making with extra care) process of purification, need to add iron sheet or scrap iron, increased production cost; The 3rd, removal of impurities is unclean, and the iron oxide yellow of production and red iron oxide finished product purity are not high; The 4th, in oxidising process, prepare crystal seed, need specialized apparatus, increased the technological process of production, improve investment and produced instinct; The 5th, produce high-purity iron oxide redly, be that impurity is removed in vacuum filtration with pure iron and sulfuric acid reaction, the copperas solution that obtains is added soda ash, obtain FeCO through the centrifugation washing and filtering
3Filter cake obtains the very high ferric oxide of purity after high-temperature calcination, the centrifugal pulverizing of whirlwind.So far do not find to produce the report of high purity iron oxide yellow and red iron oxide with by-product ferrous sulfate during production of titanium white powder.
[summary of the invention]
For overcome exist in the existing the whole bag of tricks that utilizes by-product ferrous sulfate during production of titanium white powder to produce iron oxide yellow and red iron oxide need heat, removal of impurities is clean, complex manufacturing, production cost height and the low shortcoming of product purity, the invention provides and a kind ofly be lower than in temperature under 60 ℃ the condition, utilize that byproduct ferrous sulfate of titanium dioxide solution is made with extra care, oxidation and produce the method for high-purity mangesium oxide iron oxide yellow and red iron oxide.
The technical solution adopted for the present invention to solve the technical problems is: a kind of byproduct ferrous sulfate of titanium dioxide prepares the method for iron oxide yellow and red iron oxide, mainly comprises the steps:
First step is the refining of byproduct ferrous sulfate of titanium dioxide solution: treating process comprises mainly except that titanium and removes metal ions such as dezincify, manganese, aluminium that the pH value of removing titanium process employing water dilution or dilute alkaline soln adjusting copperas solution makes titanium ion Ti greater than 1.5
3+Hydrolysis is complete, forms metatitanic acid H
2TiO
3, be lower than under 60 ℃ the condition the coarse grained metatitanic acid H of generation in temperature
2TiO
3, copperas solution is carried out filtering separation, the filtrate that obtains is for removing the copperas solution of titanium; To remove metal ions such as dezincify, manganese, aluminium again through the above-mentioned copperas solution that removes titanium then, regulate the above-mentioned pH that removes the copperas solution of titanium with basic solution and be slightly acidic, the scope of pH value is 3＜pH＜7, add oxygenant, in containing the abundant water of oxygen or when containing chlorine residue in the water, perhaps do not add oxygenant, make the ferrous Fe of being oxidized in the solution
3+And the precipitation of generation ironic hydroxide, cotton-shaped ferric hydroxide precipitate has strong adsorptive power to foreign ion during precipitation, foreign ion will produce co-precipitation, carry out filtering separation then, and the filtrate that obtains is for removing the copperas solution of metal ions such as titanium, zinc, manganese, aluminium;
Second step is oxidation: the pH value of regulating the copperas solution that obtains behind first step, be lower than in temperature that blowing air carries out oxidation under 60 ℃ the condition, ferrous oxidation is become ferric iron, in pH value scope is under 3＜pH＜7 conditions, what obtain is that iron oxide yellow also forms tiny iron oxide yellow crystal gradually, in pH value scope is under 7＜pH＜12 conditions, what obtain is that red iron oxide also forms tiny red iron oxide crystal gradually, the pH value reduces gradually simultaneously, control pH＞4 of solution then, continue the bubbling air oxidation, the fine crystals of red iron oxide is grown up gradually, forms red iron oxide;
Third step is rinsing, filtration and drying: iron oxide yellow and red iron oxide that second step is obtained add water rinse repeatedly, calcium, magnesium, sulfate radical are qualified in water, filter then, iron oxide yellow that obtains and red iron oxide are deposited in 95 ℃ of-110 ℃ of oven dry, get iron oxide yellow and red iron oxide product.
Under the situation that metatitanic acid need not utilize or metatitanic acid is few that generates, will and remove the two step removal of impurities of metal ions such as dezincify, manganese, aluminium except that titanium and be merged into a step removal of impurities, directly under the condition of the second step removal of impurities, in the described first step Ti
3+, Fe
3+Hydrolytic precipitation carries out simultaneously, saves the independent titanium lock out operation that removes.
Oxygenant described in the first step is a hydrogen peroxide, add the hydrogen peroxide add-on by volume less than 5% of copperas solution.
Basic solution described in the first step is ammoniacal liquor, sodium hydroxide or yellow soda ash.
When producing the ferric oxide series pigment of general purity, only operation removes the step of titanium in the described first step.
During the iron of oxidation described in first step precipitation, make the ferric hydroxide precipitate of absorption impurity complete with activated carbon or flocculation agent.
The metatitanic acid that obtains in the described first step adopts the dilute acid soln washing, uses water rinse, removes the iron contamination that is adsorbed on plane of crystal, in the calcining down of 600 ℃ of-800 ℃ of high temperature, obtains titanium white powder pigment.
When described whole process neutral and alkali solution adopted ammoniacal liquor to regulate the pH value of controlling solution, the ammonium sulfate that contains in the filtrate that obtains obtained byproduct of ammonium sulfate through concentrating.
Positively effect of the present invention is: the present invention is except that dry, calcining, and all the other each steps all can be carried out under temperature is lower than 60 ℃ normal temperature condition, generally are at ambient temperature, and energy consumption is low; Adopt the two step impurity removal and purifications that remove titanium and remove metal ions such as dezincify, manganese, aluminium, removal of impurities degree height can be produced highly purified iron oxide yellow and red iron oxide; Cancelled traditional second oxidation method, need not prepare crystal seed, blowing air at normal temperatures, directly ferrous oxidation has been become iron oxide yellow and red iron oxide, technical process is shorter, and production cost is low; In treating process, do not consume scrap iron, reduced cost, saved resource.
[description of drawings]
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is a technical process block diagram of the present invention.
Among the figure: the 1-refining and edulcoration, 11-removes titanium, and 12-removes metal ions such as dezincify, manganese, aluminium, 2-oxidation, 3-rinsing, filtration and drying, 4-calcining.
[embodiment]
Embodiment 1:
Byproduct ferrous sulfate of titanium dioxide prepares the method for high purity iron oxide yellow and red iron oxide, the concentration of ferrous sulfate is 20%, Titanium White Production By Sulfuric Acid Process is a main component with the ferrous sulfate in the by-product ferrous sulfate during, secondly also contains elements such as Mg, Al, Si, Ca, Ti, Zn, Ba, Mn.These elements have very big influence to the production of iron oxide yellow and red iron oxide, so the first step is exactly to refining 1 of above-mentioned copperas solution:
Have two step removal of impurities to separate in refining 1 process, in the present embodiment, two step removal of impurities are all carried out at ambient temperature, and it is to remove titanium 11 and remove other impurity that the first step removal of impurities separates, and dilute with water or dilute alkaline soln are regulated the pH value of above-mentioned solution greater than 1.5, make titanium ion Ti
3+Hydrolysis is complete, forms metatitanic acid H
2TiO
3, the hydrolysis principle can be expressed as:
Ti
3++H
2O＝H
2TiO
3
Under the condition of heating, metatitanic acid H
2TiO
3Hydrolysis reaction is rapid; At room temperature, hydrolysis time is longer, but the particle that generates is thicker, filters easily.Be lower than in temperature under 60 ℃ the condition after the hydrolysis, present embodiment is to carry out filtering separation under the condition of room temperature, and the filtrate that obtains is for removing the copperas solution of titanium.
The second step removal of impurities is to remove metal ions 12 such as dezincify, manganese, titanium, certainly after the first step refining and edulcoration 11 has been removed most of titanium, the superfine crystal that also has a small amount of metatitanic acid in the solution, need further remove, it is 5.5 that filtrate after removing titanium refining 11 is regulated the pH value with strong aqua, and add a small amount of hydrogen peroxide or bubbling air, make that a spot of ferrous oxidation becomes Fe in the solution
3+Generate the precipitation of ironic hydroxide, cotton-shaped ferric hydroxide precipitate has very strong adsorptive power to foreign ion during precipitation, and most foreign ions will produce co-precipitation.Because the ironic hydroxide that forms seldom, easily agglutination can make the ferric hydroxide precipitate of absorption impurity complete with activated carbon or flocculation agent, when using activated carbon in the present embodiment, filters more or less freely.
In this refining 1 process, if the metatitanic acid that generates need not utilize or metatitanic acid situation seldom under, two steps can be merged into a step, directly under the condition in second step 12, with Ti
3+And Fe
3+Hydrolysis, precipitation are carried out simultaneously, can save 1 lock out operation.If when producing the ferric oxide series pigment of general purity, only operation removes the step of titanium 11.
Second step was oxidation: experiment shows that not adding crystal seed can carry out oxidation equally, when having freshly prepd crystal seed to exist, can make the iron hydroxide particle of generation even, oxidation rate is also had certain influence, but also increased operation steps, has increased cost.
In order to reduce operation, the present invention does not add crystal seed in copperas solution, the pH value of regulator solution, regulating the pH value with strong aqua is 5-7, and blowing air carries out oxidation 2 at ambient temperature, and the pH value reduces gradually simultaneously, control pH value is 3-7, continue bubbling air, the iron oxide yellow crystal is grown up gradually, obtains the iron oxide yellow precipitation; Iron oxide yellow is converted into red iron oxide behind 300 ℃ temperature lower calcination, purity reaches 99.5%.
In the process of oxidation 2, be lower than in temperature under 60 ℃ the condition, blowing air oxidation 2 under different pH conditions, make the ferric iron hydrolysis can obtain different products: pH value scope is 3＜pH＜7 under solutions of weak acidity, what obtain is iron oxide yellow, pH value 7＜pH＜12 under alkaline condition, what obtain is red iron oxide.Owing to produce H in the ferric hydrolytic process
+Ion increases solution acidity gradually, in process of production, needs constantly to add alkaline aqueous solution, with pH value＞3 of solution in the controlled oxidation reaction process.
The 3rd step was rinsing, filtration and dry 3: iron oxide yellow and red iron oxide that above-mentioned steps is obtained add water rinse repeatedly, calcium, magnesium, sulfate radical etc. are qualified in water, filter, iron oxide yellow that obtains and red iron oxide are deposited in 95 ℃ of-110 ℃ of oven dry, can get iron oxide yellow and red iron oxide product.Iron oxide yellow is comparatively stable when oven dry below 120 ℃, when being heated to more than 260 ℃, can be converted into red iron oxide.
For byproduct ferrous sulfate of titanium dioxide is fully utilized, the metatitanic acid H that in dissolving of the present invention, scavenging process, obtains
2TiO
3, with the dilute acid soln washing, water rinse is removed the impurity such as iron that are adsorbed on plane of crystal, in 600 ℃ of-800 ℃ of high-temperature calcinations, obtains the fine titanium white powder pigment.
If when basic solution simultaneously of the present invention adopts ammoniacal liquor to regulate the pH value of controlling solution, contain relatively large ammonium sulfate in the filtrate that obtains, this ammoniumsulphate soln can obtain byproduct of ammonium sulfate through concentrating.
Embodiment 2:
The concentration of ferrous sulfate is 1molL in the present embodiment
-1It is 5.5 that the pH value is directly regulated with concentrated NaOH solution in the dissolving back, make titanium and ferric iron hydrolysis in the solution, filter, carry out impurity removal and purification 1, it is 3-7 that the filtrate behind impurity removal and purification 1 is regulated the pH value with 20% NaOH solution, obtain solution and be bottle-green ferrous sulfate colloid, be lower than in temperature under 60 ℃ the condition, to this colloid blowing air oxidation 2, obtain iron oxide yellow then; Iron oxide yellow is converted into red iron oxide behind 300 ℃ temperature lower calcination 4, purity is more than 96%, meets the standard of national sulfuric acid process oxygenerating iron oxide red.
The present invention is lower than in temperature under 60 ℃ the condition, byproduct ferrous sulfate of titanium dioxide solution is carried out refining and edulcoration, by adjusting the pH value of solution, reach the purpose of removing titanium and removing metal ions such as dezincify, manganese, control the pH value of solution then, blowing air carries out oxidation under normal temperature condition, under different reaction conditionss, obtains iron oxide yellow or red iron oxide; Iron oxide yellow is converted into red iron oxide behind 300 ℃ temperature lower calcination, purity reaches 99.5%.The present invention has that technical process is simple, cost of manufacture is low, and the advantage that the product purity that obtains is high is suitable for the comprehensive utilization of byproduct ferrous sulfate of titanium dioxide.
Claims (8)
1, a kind of byproduct ferrous sulfate of titanium dioxide prepares the method for iron oxide yellow and red iron oxide, it is characterized in that: mainly comprise the steps:
First step is the refining of byproduct ferrous sulfate of titanium dioxide solution: treating process comprises mainly except that titanium and removes dezincify, manganese, aluminum metal ion that the pH value of removing titanium process employing water dilution or dilute alkaline soln adjusting copperas solution makes titanium ion Ti greater than 1.5
3+Hydrolysis is complete, forms metatitanic acid H
2TiO
3, be lower than in temperature under 60 ℃ the condition, generate coarse grained metatitanic acid H
2TiO
3, copperas solution is carried out filtering separation, the filtrate that obtains is for removing the copperas solution of titanium; To remove dezincify, manganese, aluminum metal ion again through the above-mentioned copperas solution that removes titanium then, regulate the above-mentioned pH that removes the copperas solution of titanium with basic solution and be slightly acidic, the scope of pH value is 3＜pH＜7, and adds oxygenant, makes the ferrous Fe of being oxidized in the solution
3+And the precipitation of generation ironic hydroxide, cotton-shaped ferric hydroxide precipitate has strong adsorptive power to foreign ion during precipitation, and foreign ion will produce co-precipitation, carry out filtering separation then, and the filtrate that obtains is for removing titanium, zinc, manganese, aluminum metal ionic copperas solution;
Second step is oxidation: the pH value of regulating the copperas solution that obtains behind first step, be lower than in temperature that blowing air carries out oxidation under 60 ℃ the condition, ferrous oxidation is become ferric iron, in pH value scope is under 3＜pH＜7 conditions, what obtain is that iron oxide yellow also forms tiny iron oxide yellow crystal gradually, in pH value scope is under 7＜pH＜12 conditions, what obtain is that red iron oxide also forms tiny red iron oxide crystal gradually, the pH value reduces gradually simultaneously, control pH＞4 of solution then, the fine crystals of red iron oxide is grown up gradually, forms red iron oxide;
Third step is rinsing, filtration and drying: iron oxide yellow and red iron oxide that second step is obtained add water rinse, calcium, magnesium, sulfate radical are qualified in water, filter then, iron oxide yellow that obtains and red iron oxide are deposited in 95 ℃ of-110 ℃ of oven dry, get iron oxide yellow and red iron oxide product.
2, byproduct ferrous sulfate of titanium dioxide according to claim 1 prepares the method for iron oxide yellow and red iron oxide, it is characterized in that: in the described first step under the situation that metatitanic acid need not utilize or metatitanic acid is few that generates, to be merged into a step removal of impurities except that titanium with except that dezincify, manganese, aluminum metal ion two go on foot removal of impurities, directly under the condition of the second step removal of impurities, with Ti
3+, Fe
3+Hydrolytic precipitation carries out simultaneously, saves the independent titanium lock out operation that removes.
3, byproduct ferrous sulfate of titanium dioxide according to claim 1 and 2 prepares the method for iron oxide yellow and red iron oxide, it is characterized in that: when producing the ferric oxide series pigment of general purity, only operation removes the step of titanium in the described first step.
4, byproduct ferrous sulfate of titanium dioxide according to claim 1 and 2 prepares the method for iron oxide yellow and red iron oxide, it is characterized in that: oxygenant described in the first step is hydrogen peroxide or Sodium Nitrite, add the hydrogen peroxide add-on by volume less than 5% of copperas solution.
5, byproduct ferrous sulfate of titanium dioxide according to claim 1 prepares the method for iron oxide yellow and red iron oxide, it is characterized in that: during ferric hydroxide precipitate described in the first step, make the ferric hydroxide precipitate of absorption impurity complete with activated carbon or flocculation agent.
6, byproduct ferrous sulfate of titanium dioxide according to claim 1 prepares the method for iron oxide yellow and red iron oxide, it is characterized in that: basic solution described in the first step is ammoniacal liquor or sodium hydroxide.
7, byproduct ferrous sulfate of titanium dioxide according to claim 1 and 2 prepares the method for iron oxide yellow and red iron oxide, it is characterized in that: the metatitanic acid that obtains in the described first step, the washing of employing dilute acid soln, use water rinse, remove the iron contamination that is adsorbed on plane of crystal, in the calcining down of 600 ℃ of-800 ℃ of high temperature, obtain titanium white powder pigment.
8, byproduct ferrous sulfate of titanium dioxide prepares the method for iron oxide yellow and red iron oxide according to claim 1 or 5, it is characterized in that: when described whole process neutral and alkali solution adopts ammoniacal liquor to regulate the pH value of controlling solution, the ammonium sulfate that contains in the filtrate that obtains obtains byproduct of ammonium sulfate through concentrating.
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