CN1233753C - Process for preparing ferric oxide red powder - Google Patents
Process for preparing ferric oxide red powder Download PDFInfo
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- CN1233753C CN1233753C CN 03150766 CN03150766A CN1233753C CN 1233753 C CN1233753 C CN 1233753C CN 03150766 CN03150766 CN 03150766 CN 03150766 A CN03150766 A CN 03150766A CN 1233753 C CN1233753 C CN 1233753C
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- ferric oxide
- oxide red
- red powder
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Abstract
The present invention relates to a new method for producing high purity ferric oxide red powder. In the prior art, when the raw materials of ferrous iron of high manganese are processed, the defects of high production cost and low product purity are caused. In the present invention, byproduct ferrous sulphate generated in the process of the production of titanium dioxide powder is used as a raw material; high purity soft-magnetic ferric oxide red pwoder is manufactured by the processes of purification, impurity removement, precipitation, demanganizing, washing, spray burning, etc.; the impurity content of silicon, aluminum, calcium, magnesium, etc. is less than 80 ppm, the manganese content is less than 0.2%, and the Fe-[2]O-[3] content reaches more than 99.5%. The present invention has the advantages of simple technological process, low production cost and high product quality; besides, the industrial production in a large scale can be realized.
Description
Technical field
The invention belongs to the soft magnetic materials production technical field, relate to the preparation method of high purity ferric oxide rouge and powder.
Background technology
Along with the surge of information age to the magneticsubstance demand, as the main component of magneticsubstance, the demand of ferric oxide red powder grows with each passing day.As the high purity ferric oxide rouge and powder of high-end magneticsubstance, it is except requiring silicon, aluminium, and calcium, foreign matter contents such as magnesium are less than outside the 80ppm, and right manganese content also requires to be lower than 0.2%.The raw material of ferric oxide red powder is cheap ferrous salt, and its source can be divided into two big classes: the first kind belongs to hydrochloric acid system, as iron protochloride, derives from the waste acid liquor that cleans steel plate.Manganese content in the steel plate is usually less than 0.2%.The another kind of sulfuric acid system that belongs to as ferrous sulfate, derives from the by product of titanium white production.According to the source difference of raw material, its manganese content is higher than 0.2%, can reach 1-2% usually, even higher.The molysite of hydrochloric acid system is used the Ruthner flow process usually, and the roast method of promptly spraying is handled.Acquisition ferric oxide red powder when torch firing purifies spent pickle liquor to reclaim hydrogenchloride.Mostly low and middle-grade ferric oxide red powder in the market are to be produced by this method.This flow process is inapplicable to sulfuric acid system.Ferrous sulfate prepares ferric oxide red powder with the precipitator method usually.
The foreign matter content of the by-product ferrous sulfate during of titanium white production is higher relatively, calcium particularly, magnesium, silicon, aluminium, foreign matter contents such as manganese.Wherein the content of manganese reaches 1-2% usually.Because ferromanganese is the symbiosis element, chemical property is extremely close, separates quite difficulty.The method of traditional with the ferrous sulfate is raw material production high purity ferric oxide rouge and powder has two.A kind of method is the complex crystallization method.It obtains highly purified ferrous sulfate crystallization by the repeatedly complex crystallization of copperas solution, then through the high temperature roast, can obtain high purity ferric oxide rouge and powder.But the drawback of this method is the cost height, pollutes big.Though repeatedly complex crystallization can obtain highly purified ferrous sulfate, concentrated mother liquor will consume big energy during complex crystallization, produce a large amount of enrichments simultaneously the ferrous sulfate mother liquor of impurity can't utilize.Solid sulphuric acid ferrous decomposition temperature is very high, and power consumption is big, produces a large amount of form waste gas of sulfur dioxide simultaneously, atmosphere pollution.Domestic enterprise with this method production ferric oxide red powder is all eliminated by market because of expensive high pollution one after another at present.Another kind method is by the precipitation conversion, ferrous sulfate is converted to other salts such as Ferrox, ferrous hydroxide, iron protocarbonate, and then forms ferric oxide red powder through roast.The Ferrox method can demanganization, but this method is with high costs, can't compare with mutually with cheap in the market bulk product.Method by ferrous hydroxide prepares the method for ferric oxide red powder can not demanganization.Chinese patent ZL89105940.7 and CN1297006 reported to convert ferrous sulfate to method that iron protocarbonate is produced high purity ferric oxide rouge and powder, but nowadays high purity ferric oxide rouge and powder at that time can only can be regarded as low-and-medium-grade products in the raw materials market of magneticsubstance.And the method for patent report itself can not demanganization, can not be applicable to that high manganese ferrous sulfate is the production of raw material.So soft magnetism must be set about from low manganese raw material with the production of high purity ferric oxide rouge and powder at present.A large amount of ferrous sulfate by products can not be fully used, although with it is that other foreign matter content of ferric oxide red powder of feedstock production can lower, but owing to exceeding standard of manganese content, its product can only be included into low-grade soft magnetism ferric oxide red powder, can't enter middle and high-end market.
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with high manganese ferrous sulfate by product, the acquisition soft magnetism that cost is low, purity the is high method of ferric oxide red powder.
The present invention finishes by following technical scheme:
The present invention was divided into for two steps with the purification separation step of impurity.At first copperas solution is removed silicon, beavy metal impurities such as important impurity such as aluminium and zinc, copper, nickel, lead, cadmium; Then ferrous sulfate is transformed into basic carbonate iron precipitation, and impurity such as calcium, magnesium, manganese, sulphur, phosphorus, boron are stayed in the solution, they are separated with precipitated phase by washing.Because sulfate radical is a large amount of, precipitation must just can make the content of its sulphur reach requirement through careful cleaning.Clean the purified precipitation in the back roast of after pulling an oar, spraying, can obtain high purity ferric oxide rouge and powder.
The present invention has adopted the millipore filtration technology in twice scavenging process.In the scavenging process of the first step, add precipitation agent such as sodium sulphite, ammonium sulfide etc., add-on is same as the prior art.Utilize coprecipitation method that impurity such as silicon, aluminium, zinc, copper, nickel, lead, cadmium are adsorbed with solid-state form suppressed by vector flocculation agent then, use the microporous membrane of 0.5 μ m that it is separated with mother liquor at last.After separating, diameter will not exist greater than the suspended particle of 0.5 μ m in the mother liquor, can obtain preliminary scavenging solution thus.In this process, the acidity control of solution is advisable at PH=4-7.Second step added the carbon ammonium when purifying, ferrous sulfate is changed into basic carbonate iron precipitation, adopted the millipore filtration cleaning technique, and was ionic condition and stayed impurity such as calcium in the solution, magnesium, manganese, sulphur and separate.Because basic carbonate iron precipitation has stronger absorption property, and sulfate radical is dense, and cleaning step must be very careful.Under the effect of desorbing agent carbon ammonium,, sulfate radical can be reduced to the degree that product allows, thereby obtain highly purified ferrous precipitation through cleaning.The employing of twice millipore filtration technology makes the quality of highly purified ferric oxide red powder obtain guarantee.
Because ferromanganese is the symbiosis element, their chemical property is close, separates very difficult.In ferrous sulfate being converted to the sedimentary process of basic carbonate iron, manganese also can all convert simultaneously the manganous carbonate precipitation to, can't with basic carbonate iron precipitate and separate.Therefore, the present invention has adopted redox method simultaneously in the second step scavenging process.At first under suitable condition manganous sulfate is oxidized to Manganse Dioxide, makes it not generate the manganous carbonate precipitation with carbonate.Then ferrous sulfate is converted to basic carbonate iron, use formaldehyde or sulphite at last, as the demanganize agent, make manganese stay in the solution with the form of manganous sulfate again as sulphite, hydrosulphite, bisulfite etc.Can remove more than 80% of demanganize content thus, can be reduced to below 0.2%, satisfy of the requirement of high purity ferric oxide rouge and powder manganese content by 1.2% of raw material.
The preparation method that the present invention proposes, use high manganese byproduct ferrous sulfate to be raw material to produce in the production process of titanium pigment, pass through purification and impurity removal, the precipitation demanganize, washing and torch firing process prepare the soft magnetism ferric oxide red powder, behind the purification and impurity removal with the manganese oxidation, promptly under the pH=3-7.5 condition, add carbon ammonium and logical simultaneously dioxygen oxidation, make manganese not precipitate with the carbon ammonium that adds simultaneously, the carbon ammonium then converts ferrous sulfate to basic carbonate iron, add the demanganize agent then and filter after scouring basic carbonate iron precipitation, reach the ferromanganese separating effect.
The condition of above-mentioned demanganize process is as follows: carbon ammonium add-on is 0.68 to 1.26 of an iron level, and iron level can be analyzed acquisition from the scavenging solution of the first step.Reunite for reducing, improve the physical properties of product, should control the Fe of reaction solution
2+Concentration is between 30-100g/L, and pH is between 3-7.5.The add-on of demanganize agent is controlled at 1.2-12kg/ cubic meter reaction solution, and temperature of reaction is controlled at 5-70 ℃ and is advisable.
Because the ferric oxide red powder that present method is produced comes from sulfuric acid system, if clean not in placely, the content of sulfate radical can be up to about 0.5% sometimes in the finished product.As this situation appears, red iron oxide dry powder further can be passed through 5% carbon ammonium aqueous solution washing.By the permutoid reaction of carbonate and sulfate radical, can reach the purpose of effective reduction sulfate radical content.In the water washing process, calcium, magnesium, residual volumes such as sodium also can further reduce.
The fresh molysite deposition that makes is carried out 600-700 ℃ of torch firing, can obtain the soft magnetism ferric oxide red powder.
The ferric oxide red powder of method of the present invention preparation on the chemical quality index, its main content F e
2O
3Can reach more than 99.5%, major impurity content such as silicon, aluminium, calcium, magnesium, sodium etc. all are controlled at below the 80ppm, and the content of Mn is less than 0.2%, and the content of sulfate radical is less than 0.15%.The total chemical purity of product can compare favourably with the most high-grade high purity product SEW shelves of Japanese NKK company.Except high-purity chemical quality standard, product has also satisfied the certain physical performance index.Crystalline form as product is the α crystallographic system, and median size is 0.6-0.8 μ, observes its profile for oval spherical under electron microscope, and primary particle size is 0.1 μ, specific surface 6-8M
2/ g, loose specific weight 0.65-0.8g/L.The activity of ferric oxide red powder can be comparable with the high purity product of Japanese NKK company.
In sum, method provided by the invention is compared with traditional preparation method, has following advantage:
1, can use the high manganese ferrous sulfate of byproduct of titanium white production to be raw material, in the process that ferrous sulfate is converted to basic carbonate iron, solved the ferromanganese problem of phase separation, the soft magnetism of producing high purity ferric oxide rouge and powder, its quality can compare favourably with the most high-grade high purity product SEW shelves of Japanese NKK company.
2, Production Flow Chart is simple, and production cost is reduced greatly.
3, the use of millipore filtration equipment makes to be easy to control by steady quality of the present invention suitable industrial production in enormous quantities.
Embodiments more of the present invention are described in detail in following examples.All ratios and percentage ratio (%) all by weight, except as otherwise noted.Used carbon ammonium is an agricultural grade, and industrial ammonia is the water purification level, and water is deionized water.
Embodiment
Embodiment 1:
The industrial ferrous sulfate of loading onto 1.9kg in the 5L beaker of mechanical stirrer is housed to one, adds deionized water, add iron sheet 30g, in order to consume the free acid in the raw material to 4.0L.Maintain under 80-90 ℃ the condition, stirred 4 hours.After removing remaining iron sheet, add sodium sulphite 0.8g, 4.3% ammoniacal liquor 50mL condition pH=5 blasted air 30 minutes, was incubated after 0.5 hour, added 4.3% ammoniacal liquor 30mL again, added cpolyacrylamids 0.1g, standing over night after continuing to be incubated 4 hours.Filtrate gets the green filtrate of clear through 0.7 μ membrane filtration.Filtrate by analysis, Fe 57.24g/L, Mn 676mg/L, Si＜0.5mg/L, Al＜0.1mg/L, Ca 2.6mg/L.Yield 78.5%.
Embodiment 2:
To a 3M
3Reactor in inject 1.5M
3Deionized water drops into the 900kg industrial ferrous sulfate, under agitation adds sodium sulphite 1.5kg, and 4.4% ammoniacal liquor, 250 liters are warming up to 80-90 ℃ simultaneously, blast air 30 minutes, adds the 60g cpolyacrylamids, is incubated standing over night after 5 hours.Supernatant liquor filters through the millipore filter of 0.5 μ, gets the green filtrate 2.0M of clear
3Filtrate by analysis, Fe 67.9g/L, Mn 660mg/L, Si 1.3mg/L, Al 0.35mg/L, Ca 6.2mg/L, Mg 285mg/L.Yield 85%.
Embodiment 3:
The copperas solution 160mL that moves in the 500mL beaker of induction stirring after purifying by embodiment 1 is housed to one, slowly drips the aqueous solution that 100mL contains 10g carbon ammonium, aerating oxygen 30 minutes until pH3.5, slowly drips 6% ammoniacal liquor 30mL then.Add ammoniacal liquor and be warming up to 60 ℃ after 30 minutes slowly, add S-WAT 0.7g then, the temperature of keeping 60 ℃ stirred after 2 hours, added 6% ammoniacal liquor 15mL again, and regulator solution is to pH7.3.Be incubated 2 hours.Wash with the aqueous solution of the carbon ammonium of 3g/L behind the basic carbonate iron sedimentation and filtration that obtains and precipitate 3 times, wash 2 times.Be deposited in 100 ℃ of oven for drying 1 hour, and be warming up to 650 ℃ then, be incubated after 1.5 hours and take out, get ferric oxide red powder solid 10g.Yield 76.1%.The solid analysis result is as follows:
| Fe 2O 3(％) | SiO 2(％) | Al 2O 3(％) | CaO(％) | MnO(％) | SO 4(％) | |
| Raw material | ＜0.0013 | ＜0.003 | 0.0045 | 1.07 | ||
| Embodiment 3 | 99.3 | 0.010 | 0.002 | 0.002 | 0.130 | 0.474 |
Embodiment 4:
To a 3M
3Reactor in inject 1.5M
3Deionized water drops into the copperas solution 0.52M that presses after embodiment 2 purifies
3, under agitation add 0.45M
3The aqueous solution and the 0.45M that contain 38kg carbon ammonium
3The aqueous solution that contains 47kg20% ammoniacal liquor is warming up to 60 ℃, blast flow and be the 5-50 liter/minute pressurized air after 6 hours, add S-WAT 5kg, be incubated and add 0.12M again after 2 hours
3The aqueous solution that contains 22kg20% ammoniacal liquor continues ageing 2 hours to obtain basic carbonate iron precipitation.Precipitation is filtered with millipore filter, washes precipitation 3 times with the aqueous solution of the carbon ammonium of 3g/L then, washes 2 times.Precipitation after cleaning was sized mixing by 1: 1, in 650 ℃ of spraying torch firings.Get 45 kilograms of the good ferric oxide red powder of red flowability.Yield 89.1%.Solid state chemistry is analyzed as follows:
| Fe 2O 3(％) | SiO 2(％) | Al 2O 3(％) | CaO(％) | MnO(％) | SO 4(％) | Mg(％) | |
| Raw material | 0.003 | 0.001 | 0.009 | 0.878 | 0.487 | ||
| Embodiment 4 | 99.4 | 0.007 | 0.002 | 0.001 | 0.181 | 0.506 | 0.003 |
Embodiment 5:
The copperas solution 160mL that moves in the 500mL beaker of induction stirring after purifying by embodiment 1 is housed to one, slowly drips the aqueous solution that 100mL contains 7.14g carbon ammonium, aerating oxygen 30 minutes slowly drips 6% ammoniacal liquor 48mL simultaneously.Add ammoniacal liquor and be warming up to 70 ℃ after 30 minutes slowly, add S-WAT 0.46g then, the temperature of keeping 60 ℃ stirred after 2 hours, added 6% ammoniacal liquor 24mL again.Be incubated 2 hours again to obtain basic carbonate iron precipitation.Wash with water behind the sedimentation and filtration 3 times, the aqueous solution of the carbon ammonium of 3g/L is washed 2 times.Be deposited in 100 ℃ of oven for drying 1 hour, and be warming up to 650 ℃ then, be incubated after 1.5 hours and take out, get ferric oxide red powder solid 11.73g.Yield 89.3%.The solid analysis result is as follows:
| Fe 2O 3(％) | SiO 2(％) | Al 2O 3(％) | CaO(％) | MnO(％) | SO 4(％) | |
| Raw material | ＜0.0013 | ＜0.003 | 0.0045 | 1.07 | ||
| Embodiment 5 | 99.3 | 0.010 | 0.004 | 0.003 | 0.09 | 0.46 |
Embodiment 6:
Step by embodiment 3 experimentizes, but the add-on of carbon ammonium is 12.14g, and 3.8% ammoniacal liquor add-on is 11.47mL.Add sodium bisulfite 0.50g.Obtain the ferric oxide red powder solid and wash once, wash 3 times 200 ℃ of oven dry then with deionized water with 5% carbon ammonium aqueous solution.The content of manganese oxide and sulfate radical in the analysis solid, the result is as follows:
MnO(％)0.13，SO
4(％)0.24。
Embodiment 7:
Be equipped with in the 250mL beaker of induction stirring to one and put into the ferric oxide red powder 50g that makes by embodiment 3 methods, stirred 20 minutes down with 50 ℃, wash 2 times with deionized water then, in 200 ℃ of oven for drying with 100mL 5% carbon ammonium aqueous solution.Solid result by analysis is as follows:
| Fe 2O 3(％) | SiO 2(％) | Al 2O 3(％) | CaO(％) | MnO(％) | SO 4(％) | Mg(％) | |
| Embodiment 7 | 99.5 | 0.007 | 0.002 | 0.002 | 0.200 | 0.099 | 0.004 |
Embodiment 8:
Get the ferric oxide red powder 5kg that embodiment 4 methods make, ball milling is 0.5 hour in 5% carbon ammonia soln.To use 5% carbon ammonium aqueous solution more successively after the brown iron oxide taking-up, deionized water is respectively washed 2 times, and the back of sizing mixing is in 200 ℃ of spraying dryings.Solid result by analysis is as follows:
| Fe 2O 3(％) | SiO 2(％) | Al 2O 3(％) | CaO(％) | MnO(％) | SO 4(％) | Mg(％) | |
| Embodiment 8 | 99.5 | 0.006 | 0.003 | 0.003 | 0.188 | 0.149 | 0.005 |
Embodiment 9:
To one the concentration that moves in the 500mL beaker of induction stirring after purifying by embodiment 1 being housed is the copperas solution 145mL of 98.7gFe/L, slowly drips the aqueous solution that 140mL contains 15.13g carbon ammonium, slowly drips 2.6% ammoniacal liquor 250.2mL simultaneously.Regulate pH to 7.4.Behind the bubbling air 180 minutes, add 4.2g formaldehyde solution, the temperature of keeping 60 ℃ stirred 2 hours.Wash with water 3 times behind the basic carbonate iron sedimentation and filtration of producing, the aqueous solution of the carbon ammonium of 3g/L is washed 2 times.Be deposited in 100 ℃ of oven for drying 1 hour, and be warming up to 650 ℃ then, be incubated after 1.5 hours and take out, get the ferric oxide red powder solid.Solid is washed 2 times with 5% carbon ammonium aqueous solution, washes 3 times with deionized water then, in 200 ℃ of oven dry, gets the 19.46g finished product, productive rate 95.5%.Solid gets MnO (%) 0.186, SO by analysis
4(%) 0.144.
Claims (5)
1. the preparation method of a ferric oxide red powder, use high manganese byproduct ferrous sulfate to be raw material to produce in the production process of titanium pigment, pass through purification and impurity removal, the precipitation demanganize, washing and torch firing process prepare the soft magnetism ferric oxide red powder, it is characterized in that behind the purification and impurity removal the manganese oxidation, promptly under the pH=3-7.5 condition, add carbon ammonium and logical simultaneously dioxygen oxidation, make manganese not precipitate with the carbon ammonium that adds simultaneously, the carbon ammonium then converts ferrous sulfate to basic carbonate iron, add the demanganize agent then and filter after scouring basic carbonate iron precipitation, reach the ferromanganese separating effect, correlated condition is as follows:
(1) carbon ammonium add-on is 0.68 to 1.26 of an iron weight;
(2) the demanganize agent is formaldehyde or sulphite, and its consumption arrives 12kg/ cubic meter reaction solution 1.2;
Acidity [the H of (3) demanganize process
+] be controlled at pH=3-7.5;
(4) preparation process Fe
2+Concentration be controlled at 30gFe/ and be raised to the 100gFe/ liter.
2. method according to claim 1 is characterized in that in the purification and impurity removal process, the acidity control of solution is at PH=4-7.
3. method according to claim 1 is characterized in that purification and impurity removal adopts the millipore filtration technology.
4. method according to claim 1 is characterized in that washing with carbon ammonium aqueous solution after the demanganize.
5. method according to claim 1 is characterized in that the fresh molysite deposition that makes is carried out 600-700 ℃ of torch firing, can obtain the soft magnetism ferric oxide red powder.
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| CN 03150766 CN1233753C (en) | 2003-09-04 | 2003-09-04 | Process for preparing ferric oxide red powder |
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|---|---|---|---|
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357361C (en) * | 2005-08-23 | 2007-12-26 | 奚长生 | Method for preparing high purity iron oxide yellow and iron oxide red using titanium dioxide byproduct ferrous sulfate |
| RU2451705C2 (en) * | 2010-07-01 | 2012-05-27 | Общество с ограниченной ответственностью "Ярославский пигмент" | Method of producing iron phosphate-containing pigment |
| CN104045115B (en) * | 2013-10-30 | 2016-04-27 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of the ferric oxide for high-grade soft magnetic materials |
| CN109824090A (en) * | 2019-04-01 | 2019-05-31 | 中钢集团南京新材料研究院有限公司 | A method of it is prepared using titanium white by product object high-purity iron oxide red |
| CN111377484A (en) * | 2020-03-20 | 2020-07-07 | 安庆市长虹化工有限公司 | Pyrite resource recovery processing method |
| CN111634952B (en) * | 2020-07-24 | 2022-07-19 | 中钢集团南京新材料研究院有限公司 | Method for preparing iron oxide red by using ferrous sulfate as byproduct of titanium dioxide, product and application |
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