CN1045255A - Remove air oxidation process of iron in the aqueous solution and products thereof - Google Patents
Remove air oxidation process of iron in the aqueous solution and products thereof Download PDFInfo
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- CN1045255A CN1045255A CN89101208A CN89101208A CN1045255A CN 1045255 A CN1045255 A CN 1045255A CN 89101208 A CN89101208 A CN 89101208A CN 89101208 A CN89101208 A CN 89101208A CN 1045255 A CN1045255 A CN 1045255A
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Abstract
The present invention has introduced a kind of with the ferrous ion in the aqueous solution or be immersed in that metallic iron in the aqueous solution changes the form of ferric oxide into and the method for removing and obtain the red iron oxide color, be with the difference of traditional method, air as oxygenant is to be filled in the solution that does not contain solid materials by dispersion through the flotation machine impeller body of device in aeration tank, this solution is pumped to the fluidization post then, the solid materials that is contained in the there is fully contacted with it and reach the deironing purpose, has processing cycle weak point, the marked improvement that energy consumption is low, handle spent acid solution with this method and greatly reduce wherein content of chromium ion, alleviate environmental pollution, be suitable for relevant therewith chemical plant, machine works, Steel Plant adopt.
Description
The present invention uses the air of high dispersing as oxygenant, under the situation that has crystal seed to exist, with the ferrous ion oxidation in the aqueous solution with will be immersed in metallic iron corrosion in the aqueous solution, make them remove and obtain a kind of method of red iron oxide product with the form of ferric oxide with this method.
Using air oxidant, under the neutral condition, the ferrous ion oxydrolysis in the aqueous solution for being easy to sedimentation and filtering ferric oxide, is reached the purpose of deironing, is well-known.The method of this deironing is commonly referred to the oxidation neutralisation.Wait so long " disc type air oxidation process " (ACTA Scientiae Circumstantiae of processing steel alloy spent pickle liquor of people research of Cheng Zhi, 1983,3(4) 382), " goethite process " in " the red ammonium method " of Qingdao steel mill test processing straight carbon steel sulfuric acid pickling waste liquid and the zinc hydrometallurgy iron in the zinc sulfate solution removed with the form of pyrrhosiderite all is to belong to the oxidation neutralisation.When iron filings are immersed in the water that contains crystal seed, and blast air at a certain temperature, just the iron rust erosion can be iron oxide pigment.The wet processing of Here it is traditional manufacturing iron oxide pigment.For the iron in the ilmenite is removed, it is earlier iron to be reduced to metal form that a kind of method is arranged, and with air the metallic iron corrosion is come out in the aqueous solution then.Here it is makes " reduction-rusting process " of rich titanium material from ilmenite.This method is the same with the wet processing of making iron oxide pigment in essence.With the ferrous ion in the atmospheric oxidation aqueous solution or be immersed in metallic iron in the aqueous solution, airborne molecular oxygen is dissolved in the water and works.Therefore, air height being disperseed with increase gas-to-liquid contact area, thereby guarantee in the aqueous solution enough molecular oxygens are arranged, is the key that influences oxidising process speed.Though air itself need not spend money on, inflate air in the solution, require the expenditure of energy.If air dispersion gets bad, in order to guarantee the concentration of molecular oxygen in the aqueous solution, often have to increase the speed that charges into of air, or high degree of agitation.This has not only increased the energy expenditure of inflation itself, and has increased evaporation of water.A large amount of evaporations of water, and make up water is heated to temperature required, also consume more energy, and the energy expenditure of high degree of agitation also is considerable.For example, handle in the production of ilmenite at general reduction-rusting process, the energy that the corrosion operation is consumed accounts for 2/3 of whole process energy consumption, so, no matter from unit time unit equipment volumetrical treatment capacity,, charge into and the quality of dispersion air still from energy expenditure, in with oxidation neutralisation or bubble method, be an important economic factors.Charge into the quality of air, measure with air utilization ratio.It is the air capacity of the required stoichiometric quantity of iron protoxide ion or corrosion metals iron in the solution in unit volume the unit time and the ratio of the actual air capacity that charges into.
Aforementioned each technology, because air dispersion gets badly, so reaction time is long, a little less than the processing power, air utilization ratio is low.For example the oxidation cycle of " red ammonium method " reaches 100 hours, and processing power also has only 0.035 kilogram, iron/rice
3Divide.Make traditional wet processing of iron oxide pigment for another example, be oxidized to long period and reach about 1 week unexpectedly.That yes is low-down for their air utilization ratio.For example the air utilization ratio of " red ammonium method " does not also reach 3%.The general reduction-rusting process of producing rich titanium material from ilmenite is produced, have plenty of at corrosion groove inwall installing flow-stopping plate, and with the fierce mixture that stirs reduced ilmenite and water of turbine type stirring arm, although come dispersion air to pay huge energy expenditure in such a way and corrosion device very important washed away infringement, but yet just be applicable to the superior in quality raw material that is commonly called as to the salt water ore deposit, and when the ilmenite as raw material is the fresh water ore deposit that is commonly called as, even, also still can not obtain qualified rich titanium material from qualified reduced ilmenite more than the corrosion time lengthening to 40 hour.
One of purpose of the present invention is: employing can make air height dispersive simple device, ferrous ion in the aqueous solution or the metallic iron that is immersed in the aqueous solution are changed into the form of ferric oxide and remove and obtain the red iron oxide product, so that improve the processing cycle of air utilization ratio and then shortening oxidation neutralisation and bubble method deironing, cut down the consumption of energy; Another object of the present invention is to, during ferrous ion in treating water solution, particularly when handling the steel alloy spent pickle liquor, air oxidant with high dispersing removes to handle this waste liquid to eliminate the pollution of waste liquid to environment greatly, reduce the concentration of chromium ion in the waste liquid, and then the iron in the waste liquid is become iron oxide pigment.
The present invention adopts the device of the impeller body of subaeration flotation machine general on the mineral mining processing industry as dispersion air and stirred solution in oxidation neutralisation and the bubble method.Impeller body is simple in structure, has bought the commodity of various processing poweies especially easily on market.The volume of oxidation trough only needs with the impeller body coupling just passable, does not need to add other device.So there is not the problem of groping amplification rule in the inflation mechanism that the present invention is used.For the solid materials that is immersed in the aqueous solution, the present invention adopts and just the aqueous solution is inflated, the aqueous solution that will be inflated is sent to the way dispersion air with the solid materials effect then, for this reason, the present invention is contained in the flotation machine impeller body in the aeration tank that has only the aqueous solution, and will treat that the solid materials of corrosion is contained in the fluidization post.Aeration tank and fluidization post are through the water pump polyphone.For this reason, the solution that has been inflated is injected the fluidization post by water pump, make the solid materials corrosion there and stir, the light phase that overflows from the fluidization column top flows to aeration tank again and is inflated, this and traditional oxidation neutralisation and bubble method deironing have very big difference, for example, when iron filings are made iron oxide pigment, be difficult to directly that application machine stirs dispersion air in the oxidation trough of iron filings is housed, therefore normally stir, so long processing period.
Usually, contain chromium in the steel alloy spent pickle liquor and be about 0.5 grams per liter, contain free sulfuric acid and be about 5～10%.The present invention makes chromium and a part of precipitation of iron ions with the free acid effect in waste iron filing (for example lathe iron filings) and the spent pickle liquor.Such operation also makes the concentration of the ferrous ion in the waste liquid obtain increasing, and the content of free acid is reduced.So, under all constant situation of the energy of processed waste liquid amount and consumption and oxidation neutralising arrangement, can obtain some iron oxide products more and consume a little neutralizing agents less, and the concentration that can make chromium is reduced to below 0.4 grams per liter, acidity is reduced to PH2～3 Here it is the treatment process of giving of waste liquid, then by aforementioned way with the reacted solution natural filtration.With under impeller body dispersion air and the well-beaten situation, will give spent pickle liquor after the processing and the aqueous solution of alkaline matter controlledly is added in the oxidation neutralizing well through above-mentioned.In the oxidation neutralizing well, fill the water that contains the crystal seed for preparing by iron trichloride of certain volume.Calculate by iron content, in the water as waste liquid in the oxidation neutralizing well, seed concentration be 0.2～1.6 gram iron/liter, preferably 0.7～0.8 gram iron/liter.Also contain acetic acid in the end liquid, the concentration of acetic acid is 0.1～0.8 grams per liter, preferably 0.6～0.8 grams per liter, alkaline matter as neutralizing agent, sodium hydroxide or yellow soda ash or volatile salt can, but from every mole price, the most agricultural fertilizer ammoniacal liquor of handy lower concentration.The aqueous solution and the ammoniacal liquor that contain ferrous ion are to add by the pipe that is inserted in the reacting solution respectively.The outlet of this two tubes is respectively facing to the suction port of impeller body.In the oxidation N-process, holding temperature is 80～100 ℃, and preferably 80～85 ℃, in the process, the pH value of mixture is controlled at 3.5～5.0, and for the aqueous solution of the ferrous ion that does not contain heavy metal ion such as chromium, pH value preferably is controlled at 3.5～4.0; For the aqueous solution that contains chromium, pH value preferably is controlled at 4.5～5.0.
For the material of solid form, corrosion method of the present invention is: the solid fine granular materials with metal iron filings or containing metal iron is placed in the fluidization post.Impeller body is contained in the aeration tank, as the water of medium, is in aeration tank and the circulation of fluidization intercolumniation through water pump.When for when iron filings are made red iron oxide, the end liquid of the composition of recirculated water during with above-mentioned processing sulfur acid ferrous waste liquid is the same, and the temperature of controlling in the process also is.When in order from reduced ilmenite the metallic iron corrosion to be come out, before reaction, having added the temperature of controlling in small amount of hydrochloric acid and the process in the recirculated water is about 70 ℃.The concentration of hydrochloric acid is 1～1.5%.In addition, when the corrosion reduced ilmenite, can contain crystal seed in the end liquid, but preferably contain crystal seed; Total iron amount of the contained crystal seed of end liquid is about 1/30 of contained metallic iron in the reduced ilmenite for the treatment of corrosion.
So, utilize the air oxidant of high dispersing, with the ferrous ion in the aqueous solution or be immersed in the method that ferric oxide red colorant was removed and then obtained to form that metallic iron in the aqueous solution is converted into ferric oxide, the traditional oxidation neutralisation and the processing cycle of bubble method deironing have been shortened greatly, reduced consumption, and make the iron of different grade different shapes or iron ore be fully used, greatly reduce the concentration of chromium ion in the waste liquid, thereby eliminated the pollution of waste liquid environment.
Embodiment 1
In glass beaker, the existing crystal seed and 1 liter of the acetic acid blended aqueous solution by iron trichloride preparation.The iron and the acetic acid that contain crystal seed in this end liquid all are about 0.8 grams per liter, and the impeller body of subaeration flotation machine that with its impeller diameter is 45 millimeters is as agitator.Air is sucked and is dispersed in the solution by impeller body.Stirring and holding temperature is that 85 ℃ and pH value are under 3.5～4.0 the condition, with 0.034 gram, iron/rise the flow of branch, the aqueous solution and the weak ammonia of inflow ferrous sulfate in end liquid.In the reaction process, make up water remains unchanged the volume of reaction mixture discontinuously.After so carrying out 360 minutes, stop reinforced and stirring, take out reaction mixture.The red iron oxide that suspends in the mixture is rapid sedimentation when leaving standstill.The quality of the red iron oxide that obtains meets the regulation of GB 1863-80 about mixed acid process iron oxide red standard H102 in the wet method iron oxide red.
Embodiment 2
Except through the air suction pipe of impeller body to reaction mixture by 0.9 liter, the flow that the flow of air/rise branch charges into air and adds ferrous sulfate aqueous solution is 0.15 gram, iron/liter exceptionally, other condition is identical with embodiment.Obtain meeting the red iron oxide of H102 quality standard after 288 minutes.Air utilization ratio is 8.3%.
Embodiment 3
Except the flow of ferrous sulfate aqueous solution is 0.35 gram, iron/rise outside branch and the aeration speed difference, other condition obtains meeting the red iron oxide of H102 quality standard after 2,292 minutes with embodiment.
Embodiment 4
At 1 meter
3Iron content, chromium and hydrionic concentration are respectively and drop into the machined into waste iron filing in the steel alloy sulfuric acid pickling waste liquid of 56,0.45 and 2.03 grams per liters, and feed superheated vapour.When the temperature of solution reaches 40～50 ℃, stop logical steam.When the acidity of solution is reduced to PH2～3, remove residue in the solution with natural filtration, Fe in the filtrate that obtains, the concentration of Cr is respectively 112 and 0.39 grams per liter.
Embodiment 5
In the oxidation neutralizing well, fill 0.5 meter
3The end liquid that composition and embodiment 1 are identical.The impeller diameter of impeller body is 250 millimeters, by the operation of embodiment 2 filtrate that embodiment 4 obtains is carried out the oxidation neutralizing treatment.The flow of ferrous sulfate is 0.109 kilogram, iron/rice
3Divide, aeration speed is 27.8 meters
3/ rice
3Hour, control PH is the red iron oxide that obtains meeting the first grade quality of H102 standard code after 4.5～5.0,190 minutes in the process, air utilization ratio is 11.5%.
Embodiment 6
Processed steel alloy sulfuric acid pickling waste liquid gives processing by embodiment 4 earlier, the concentration of iron, chromium, cobalt, manganese and titanium dioxide in the ferrous sulfate aqueous solution that obtains, be respectively 95.5,0.39,0.053,0.042,0.02 and 0.039 grams per liter with and pH value be 2.5, except the flow of waste liquid is 0.12 kilogram, iron/rice
3Divide, aeration speed is 43.4 meters
3/ rice
3Outside hour, other condition is with embodiment shut-down operation after 5,170 minutes.The concentration of iron, chromium, cobalt, manganese and titanium dioxide is respectively 31,0.2 in the mother liquor of the red iron oxide that obtains, and 2,0.56 6.5 and 0.58 millimeters/liter and pH value are 5.0, and the red iron oxide that obtains meets the first grade quality standard of H102 regulation.This routine air utilization ratio is 8.2%.
Embodiment 7
At diameter is 125 millimeters, and volume is in 1 liter the glass beaker, fills 300 grams and (contains T by the fresh water ore deposit through the reduced ilmenite that reduction obtains
iO
263.18), 900 milliliters in (36%) 34 milliliter of hydrochloric acid and water under 70 ℃, they are 50 millimeters impeller body inflation and stirred 25.5 hours that to its impeller diameter it is 87.7% that the rich titanium material that obtains contains titanium dioxide.
Embodiment 8
Except the diameter of beaker is 90 millimeters and contains in water by outside the crystal seed of iron trichloride preparation (about 0.8 gram, iron/liter), other is with embodiment 9, inflate and stir 24 hours after, it is 89.5% that the rich titanium material that obtains contains titanium dioxide.
Embodiment 9
Device by the fluidization post of glass control and embodiment 8 is contacted through water pump, in the fluidization post, fill reduced ilmenite 600g as embodiment 7, in 2500 milliliters recirculated water, be added with crystal seed and 80 milliliters of technical hydrochloric acids by the iron trichloride preparation, be under 70 ℃ the situation in the temperature in aeration tank inflation and fluidization post, water pump injects the bottom of fluidization post with the water in the aeration tank, and makes reduced ilmenite there be in " fluidised form ".Gently overflowing in the aeration tank mutually of capital.After so carrying out 2.5 hours and 6 hours, be respectively 13.6% and 3.8% by containing metal iron in the reduced ilmenite of corrosion.
Embodiment 10
Device is with embodiment 9, and as different from Example 9, the composition that is placed with the preceding solution of waste iron filing and reaction in the fluidization pipe is same with the end liquid phase of embodiment 1.Inflation and loop solution obtained red iron oxide after 20 hours.
Claims (6)
1, a kind of air oxidation process of removing iron in the aqueous solution and products thereof, it is a kind of air oxidant of using, with the ferrous ion in the aqueous solution or be immersed in that metallic iron in the aqueous solution changes the form of ferric oxide into and the method for removing and obtain the red iron oxide product, it is characterized in that, for the ferrous ion in the aqueous solution, be that impeller body through subaeration flotation machine is charged into the aqueous solution by dispersion as the air of oxygenant; For the metallic iron that is immersed in the aqueous solution, air is to be filled in the solution that does not contain solid materials by dispersion through the flotation machine impeller body of device in aeration tank, the solution that has been inflated, injected the fluidization post by water pump, make to be contained in fully being contacted with the aqueous solution by the solid materials of corrosion of there, the vertical solution that does not contain solid materials of fluidization post then overflows in the aeration tank.
2, air oxidation process of removing iron in the aqueous solution according to claim 1 and products thereof, particularly remove air oxidation process of ferrous ion in the aqueous solution and products thereof, it is characterized in that, for handle the steel alloy sulfuric acid pickling waste liquid be with the impeller body of flotation machine will through it air dispersion and fill in the reaction soln also stirred solution, the pH value of control reaction soln be 4.5～5.0 and temperature be under 80～85 ℃ the situation, to be added to through the aqueous solution of the steel alloy sulfuric acid pickling waste liquid that gives processing and alkaline matter in the aqueous solution that contains by the crystal seed of iron trichloride preparation and acetic acid, thereby remove the ferrous ion in the solution and obtain red iron oxide and make the solution after handling contain chromium less than 0.0002 grams per liter.
3, air oxidation process of removing ferrous ion in the aqueous solution according to claim 2 and products thereof, it is characterized in that, when handling the steel alloy sulfuric acid pickling waste liquid, contain pickle solution and the waste iron filing effect of remaining acid, make chromium content in the waste liquid reduce to 0.4 grams per liter following with make pH value reduce to 2～3.
4, air oxidation process of removing ferrous ion in the aqueous solution according to claim 2 and products thereof is characterized in that, when handling the steel alloy sulfuric acid pickling waste liquid, the concentration of described crystal seed be 0.2～1.0 gram iron/liter, preferably 0.8 gram iron/liter; The concentration of acetic acid is 0～1.0 grams per liter, preferably 0.8 grams per liter.
5, air oxidation process of removing ferrous ion in the aqueous solution according to claim 2 and products thereof, it is characterized in that, when handling the steel alloy sulfuric acid pickling waste liquid, described process is given the steel alloy sulfuric acid pickling waste liquid of processing and the aqueous solution of alkaline matter is to be added in the reaction soln by two pipes that are inserted in the reaction soln respectively, and the outlet of pipe faces toward the suction port of flotation machine impeller body respectively.
6, according to claim 1ly remove that the atmospheric oxidation of iron relates to its product in the aqueous solution, particularly remove air oxidation process that is immersed in the metallic iron in the aqueous solution and products thereof, it is characterized in that, for removing the metallic iron in the reduced ilmenite or changing iron filings into iron oxide pigment, be that reduced ilmenite or iron filings are contained in the procedure post described in the claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89101208A CN1045255A (en) | 1989-03-02 | 1989-03-02 | Remove air oxidation process of iron in the aqueous solution and products thereof |
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| CN89101208A CN1045255A (en) | 1989-03-02 | 1989-03-02 | Remove air oxidation process of iron in the aqueous solution and products thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050344C (en) * | 1996-10-24 | 2000-03-15 | 冶金工业部长沙矿冶研究院 | Method and device for continuously producing high-purity iron oxide |
| CN103184345A (en) * | 2013-03-26 | 2013-07-03 | 昆明贵金属研究所 | Method for removing iron and enriching platinum group metals from smelted iron trapping material |
| CN105800838A (en) * | 2016-05-30 | 2016-07-27 | 张石海 | Method for treating stainless steel pickling waste liquid |
-
1989
- 1989-03-02 CN CN89101208A patent/CN1045255A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050344C (en) * | 1996-10-24 | 2000-03-15 | 冶金工业部长沙矿冶研究院 | Method and device for continuously producing high-purity iron oxide |
| CN103184345A (en) * | 2013-03-26 | 2013-07-03 | 昆明贵金属研究所 | Method for removing iron and enriching platinum group metals from smelted iron trapping material |
| CN105800838A (en) * | 2016-05-30 | 2016-07-27 | 张石海 | Method for treating stainless steel pickling waste liquid |
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