CN100357192C - Deferrization method of iron-containing liquor - Google Patents
Deferrization method of iron-containing liquor Download PDFInfo
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- CN100357192C CN100357192C CNB2006100331052A CN200610033105A CN100357192C CN 100357192 C CN100357192 C CN 100357192C CN B2006100331052 A CNB2006100331052 A CN B2006100331052A CN 200610033105 A CN200610033105 A CN 200610033105A CN 100357192 C CN100357192 C CN 100357192C
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 257
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 120
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 23
- 241000231392 Gymnosiphon Species 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000002699 waste material Substances 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- -1 ammonium ions Chemical class 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 229910052935 jarosite Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Compounds Of Iron (AREA)
Abstract
The present invention relates to a deferrization method of iron-containing liquor, which solves the defect that the existing method needs high temperature condition and has low deferrization efficiency. The method comprises three steps of oxidizing the iron-containing liquor for pretreatment, preparing yellow iron crystal seed and removing iron, wherein the present invention has the iron removing step that the yellow iron crystal seed liquor is filled into a reactor, and then, the oxidized iron-containing liquor and weak base liquor are simultaneously dripped into the reactor. When the reacting liquor volume achieves the effective volume of the reactor, the reacting liquor is extracted out of the reactor and filtered. The filtering liquor is the desired liquor removing the iron. The method of the present invention can be applied to the deferrization of different iron-containing liquor. The present invention has the advantages of high reaction speed, high deferrization efficiency, simple integral process, easy operating condition control and little equipment investment during the reaction under normal temperature.
Description
Technical Field
The invention relates to a method for removing iron from an iron-containing solution.
Background
The basic processes for removing iron from iron-containing solutions include the jarosite process, goethite process, hematite process, Fe (OH)3Precipitation method. The disadvantages of these methods are as follows:
the jarosite method requires that enough sulfate ions and alkali metal or ammonium ions are contained in the solution, the reaction temperature is 85-100 ℃, the iron removal is not thorough, the concentration of the residual iron is more than 0.2g/L generally, the pH control range is narrow, the control is difficult, the residue amount is large, and the reaction time is long. Goethite method requires reaction temperature of 70-100 deg.C, oxidation at high temperature, reduced oxygen solubility, low oxygen utilization efficiency, and Fe in initial solution3+The concentration is less than 1g/L, and if the concentration is higher than the concentration, a reduction step is required to be added; the hematite method requires higher temperature, 180-200 ℃, and needs pressurizing equipment. Fe (OH)3The precipitation method is colloidal and difficult to filter, and can adsorb a large amount of other metals for coprecipitation.
The above summary comes from a comprehensive reading of the following documents: CN1285416A, 1237641A, 1093756A, 1041339A, 1337360A, 1216517A, 1033786A, chemical metallurgy vol.21, No.3, p294, molybdenum industry of China vol.25, No.1, p46, chemical world No.6, p289, mining and metallurgy engineering vol.16, No.3, p48, vol.19, No.4, p40, hydrometallurgy No.6, p30, university of south China school of Industrial science vol.31, No.5, p419, university of Kunming technology university vol.21, No.6, p 140.
Disclosure of Invention
The invention aims to provide a method for removing iron from an iron-containing solution, which has reaction at normal temperature and high iron removal efficiency, aiming at the problems of the existing iron removal method.
The invention comprises the following steps:
(1) pretreatment of the iron-containing solution: oxidizing the iron-containing solution to cause Fe in the iron-containing solution2+Is completely oxidized into Fe3+Then adding alkali to adjust the pH value of the solution to 1;
(2) preparing iron yellow seed crystals;
(3) iron removal: firstly, adding an iron yellow seed crystal solution which is prepared from the iron yellow seed crystal prepared in the step (2) and contains iron of not less than 15g/L into a reactor, stirring, then simultaneously dropwise adding the iron-containing solution and the weak base solution oxidized in the step (1), wherein the value L/min of the maximum dropwise adding speed of the iron-containing solution is less than V/5c, the dropwise adding speed of the weak base solution is determined by controlling the pH value of the solution to be 3-5.5, when the volume of the reaction solution reaches the effective volume of the reactor, extracting the reaction solution from the bottom of the reactor, and filtering to obtain a filtrate which is the required iron removal solution; the weak base solution is Na with different concentrations2CO3Ammonium carbonate, ammonia water, K2CO3、NaHCO3、KHCO3、NH4HCO3One or a mixture of two or more of them, wherein V is the effective volume of the reactor, and c is the iron content g/L in the iron-containing solution.
In step (1) of the present invention, the oxidation of the iron-containing solution may be carried out by first oxidizing with air and then deeply oxidizing with an oxidizing agent, or directly oxidizing with an oxidizing agent. The chemical reactions that occur upon oxidation by air are:
4Fe2++O2+4H+＝4Fe3++2H2O
from this equation, the theoretical required oxygen consumption can be calculated. The oxidant can be selected from H2O2、Cl2、KClO3、NaClO、NaClO3One of them. Determination of Fe in iron-containing solution2+Whether or not to be finishedTotal oxidation, using potassium ferricyanide for spot experiments, if there is no blue precipitate, indicating Fe2+Is completely oxidized.
The reaction seed crystal in the step (3) can adopt α type, β type or r type iron yellow seed crystal, and the invention can adopt various existing methods to prepare α type, β type or r type iron yellow seed crystal in the step (2).
r type ironThe yellow seed crystal can be prepared by the following method: firstly, mixing a mixed solution of ethylenediamine tetraacetic acid, copperas and water according to the weight ratio of 2: 50-100: 1000, and stirring until the copperas are completely dissolved; then, 2-4mol/L ammonia water or Na with the concentration of 10-15 percent is added dropwise2CO3Dropwise adding the solution at the speed of 1-4L/hour/20L of copperas solution until the pH value of the solution is equal to 8.2-8.7, and stopping dropwise adding ammonia water; and after continuously stirring for 10-20 minutes, starting introducing oxygen for oxidation, after the pH value is reduced to 4 and stabilized, continuously dropwise adding ammonia water, adjusting the pH value to 5, stopping dropwise adding ammonia water, gradually reducing and stabilizing the pH value along with the progress of oxidation reaction, dropwise adding ammonia water for a period of time, gradually increasing the pH value to 7, at the moment, stabilizing the pH value, stopping dropwise adding ammonia water without reducing along with the prolonging of the reaction time, after continuously stirring for 15-20 minutes, stopping introducing oxygen, standing and aging for 1 hour, and filtering to obtain the r-type iron yellow crystal seed.
The main reactions occurring in the preparation process of the r-type ferrite yellow seed crystal are as follows:
Fe2++2OH-+1/4O2→r-FeOOH+1/2H2O
in the step (3) of the present invention: the stirring speed is preferably 60 r/min; the adding amount of the iron oxide yellow seed crystal solution is 1/4 of the effective volume of the reactor; the value of the dropping speed L/min of the iron-containing solution is preferably V/15c to V/8 c. The dripping speed of the weak base solution is determined by controlling the pH3-5.5 of the solution, the specific range of the pH valueis mainly determined by the type of the iron-containing solution, if the weak base solution is waste liquid containing copper and iron, the correspondingly controlled pH value is lower and is 3-3.4, if the weak base solution is waste liquid containing manganese and iron, the correspondingly controlled pH value is higher and is 4.5-5.0.
The invention can adopt a continuous reaction mode or an intermittent reaction mode: and (3) adopting a continuous reaction mode, after the volume of the reaction liquid reaches the effective volume of the reactor in the step (3), starting to extract the reaction liquid from the bottom of the reactor, and continuously dropwise adding the iron-containing solution and the weak base solution at the same time, wherein the extracted volume of the reaction liquid is equal to the sum of the dropwise adding volumes of the iron-containing solution and the weak base solution, so that the volumes of the solutions entering and exiting the reactor are equal. And (3) stopping dropwise adding the weak alkali solution and the iron-containing solution after the volume of the reaction solution reaches the effective volume of the reactor in the step (3), continuously stirring for 5-10 minutes, standing and settling for 10-15 minutes, extracting 3/4 reaction solution with the effective volume of the reactor from the reactor, filtering to obtain an iron-removing solution, and after the first batch of reaction is finished, remaining 1/4 seed crystal mixed solution with the effective volume of the reactor in the reactor to perform the next batch of reaction. And the iron residue is lower by adopting a batch reaction mode.
For continuous reaction mode, such as iron content of iron-containing solution is less than 10g/L or iron yellow seed content of reactor is less than 10g/L, iron yellow filter cake obtained by filtering is crushed and added into reactor to supplement seed crystal.
For batch mode, if the iron oxide yellow seed crystal content in the remaining mixed liquid is lower than 15g/L, the iron oxide yellow filter cake obtained by filtering needs to be crushed and added into the reactor to replenish the seed crystal.
The invention has the following advantages: the method is carried out at normal temperature, saves energy, has easily controlled reaction conditions, high reaction speed, high iron removal efficiency, low iron residue, easy filtration of precipitate, less adsorption and co-precipitation, simple overall process, easily controlled operation conditions and small equipment investment; the filter cake can be calcined into common iron oxide red after washing and impurity removal, so that the waste is recycled and the waste is changed into valuable.
Detailed Description
The first embodiment is as follows:
iron removal of waste liquid containing nickel, cobalt and iron in enterprises producing nickel sulfate and cobalt.
The waste liquid comprises the following components: total iron Fe: 13.49g/L, Ni2+.90.82g/L，Co2+：13.47g/L
Firstly, preparing iron yellow seed crystal:
weighing EDTA, Melanteritum, and water with mass of 2kg, 50kg, and 500kg respectively, and mixingStirring until the copperas is completely dissolved; then, slowly dropwise adding 2mol/L ammonia water at a dropwise adding speed of 70L/hour until the pH value of the solution is 8.5, and stopping dropwise adding the ammonia water; after stirring for 15 minutes, starting oxygen introduction for oxidation until the pH value is reduced to about 4 and is stable, continuing to dropwise add ammonia water, adjusting the pH value to about 5, stopping dropwise adding ammonia water, gradually reducing and stabilizing the pH value along with the progress of the oxidation reaction, dropwise adding ammonia water for a period of time, gradually increasing the pH value to about 7, and indicating that the pH value is stable and does not reduce along with the extension of the reaction time, which indicates that Fe2+And (3) completely oxidizing the iron oxide yellow to generate iron oxide yellow, stopping dropwise adding ammonia water, continuing stirring for 15 minutes, stopping introducing oxygen, standing and aging for 1 hour, and filtering to obtain the r-type iron oxide yellow seed crystal.
II, iron removal:
adding hydrogen peroxide to remove Fe in the waste liquid2+Is completely oxidized into Fe3+Judgment of Fe2+If the iron is completely oxidized, the spot experiment is carried out by potassium ferricyanide, if no blue precipitate exists, the Fe is shown2+Is completely oxidized, and then Na with the concentration of 30 percent is added2CO3After the pH of the solution was adjusted to 1, 500L of a freshly prepared iron yellow seed crystal solution (containing about 20g/L iron) was added to a 2000L reactor, stirred at a rate of 60r/min, and simultaneously dropwise added with a waste solution oxidized with hydrogen peroxide and Na having a concentration of 15%2CO3The dropping speed of the solution and the waste liquid is about 800L/hour, Na2CO3The dropping speed of the solution is about 400L/hour, the pH of the solution in the reactor is controlled to be 4.5-4.8, and after 75 minutes of reaction, the dropping of Na is stopped2CO3Stirring the solution and the waste liquid for 5-10 min, standing for 10 min, pumping the reaction liquid into a plate-basket filter press for filter pressing, and leaving about 500L of the liquid crystal in the reactorRight, start the next batch of reaction. After four continuous batches of reactions, the iron content of the filtrate is determined to be less than 3mg/L, the iron removal rate reaches 99.98%, and after washing and drying, the nickel content of the filter cake is less than 0.5% and the cobalt content is less than 0.3%.
Example two:
iron removal of manganese-containing solution of manganese sulfate production enterprises.
The components of the solution are as follows: total iron Fe: 13.18g/L, Mn2+：49.91g/L。
Firstly, preparing iron yellow seed crystal: the same as the first embodiment.
II, iron removal:
adding hydrogen peroxide to remove Fe in manganese-containing solution2+Is completely oxidized into Fe3+Reuse Na2CO3After the pH of the solution was adjusted to about 1, 500L of a freshly prepared iron yellow seed solution (containing about 20g/L iron) was added to a 2000L reactor, and the mixture was stirred at a rate of 60r/min while adding dropwise the oxidized manganese-containing solution and 15% Na2CO3The dropping speed of the solution containing manganese is about 1000L/hour, Na2CO3The dropping speed of the solution is about 500L/hour, the pH of the reaction solution is controlled to be 4.5-5.0, and after the reaction is carried out for 60 minutes, the dropping of Na is stopped2CO3And stirring the manganese-containing solution for 5 to 10 minutes, standing for 15 minutes, pumping the reaction solution into a plate and basket filter press for filter pressing, and starting the next batch of reaction after about 500L of the residual liquid crystal in the reactor. After four continuous batches of reactions, the iron content of the filtrate is determined to be lessthan 2mg/L, the iron removal rate reaches 99.98%, and the manganese content of the filter cake after washing and drying is less than 0.3%.
If a continuous reaction mode is adopted, after the volume of the reaction liquid reaches the effective volume of the reactor, the reaction liquid is pumped out from the bottom of the reactor, and the iron-containing solution and the weak base solution are continuously and simultaneously dripped, wherein the pumped volume of the reaction liquid is equal to the sum of the dripped volumes of the iron-containing solution and the weak base solution, so that the volumes of the solutions entering and exiting the reactor are equal; filtering the extracted reaction liquid to obtain filtrate, namely the needed iron removal solution; after continuous reaction for 3 hours, the iron content of the filtrate is determined to be less than 6mg/L, the iron removal rate reaches 99.93 percent, and the manganese content of the filter cake after washing and drying is less than 0.3 percent.
Example three:
iron removal of zinc-containing solution of zinc oxide production enterprises.
The components of the solution are as follows: total iron Fe: 11.53g/L, Zn2+：68.42g/L。
Firstly, preparing iron yellow seed crystal: the same as the first embodiment.
II, iron removal:
adding KClO3Fe in zinc-containing solution2+Is completely oxidized into Fe3+Reuse Na2CO3After the pH value of the solution is adjusted to about 1, 500L of newly prepared iron yellow seed crystal solution (containing about 20g/L of iron) is added into a 2000L reactor, the solution is stirred at the speed of 60r/min, meanwhile, oxidized zinc-containing solution and ammonia water with the concentration of 6 percent are dripped, the dripping speed of the zinc-containing solution is about 680L/hour, the flow dripping speed of the ammonia water is about 320L/hour, the pH value of the reaction solution is controlled to be 4.0-4.5, after the reaction is carried out for 90 minutes, the dripping of the ammonia water and the zinc-containing solution is stopped, the reaction solution is kept stirring for 5-10 minutes, then the reaction solution is kept still for 10 minutes, the reaction solution is pumped into a plate basket filter press to be subjected to filter pressing, about 500L of residual crystal liquid in the reactor. After four continuous batches of reactions, the iron content of the filtrate is determined to be less than 5mg/L, the iron removal rate reaches 99.95 percent, and the zinc content of the filter cake after washing and drying is less than 0.3 percent.
Claims (9)
1. A method for removing iron from an iron-containing solution is characterized by comprising the following steps:
(1) pretreatment of the iron-containing solution: oxidizing the iron-containing solution to cause Fe in the iron-containing solution2+Is completely oxidized into Fe3+Then adding alkali to adjust the pH value of the solution to 1;
(2) preparing iron yellow seed crystals;
(3) iron removal: firstly, adding an iron yellow seed crystal solution which is prepared from the iron yellow seed crystal prepared in the step (2) and contains iron of not less than 15g/L into a reactor, stirring, then simultaneously dropwise adding the iron-containing solution and a weak base solution oxidized in the step (1), wherein the value of the maximum dropwise adding speed L/min of the iron-containing solution is smaller than V/5c, the dropwise adding speed of the weak base solution is determined by controlling the pH value of the solution to be 3-5.5, when the volume of the reaction solution reaches the effective volume of the reactor, extracting the reaction solution from the bottom of the reactor, and filtering to obtain a filtrate which is the required iron removal solution; the weak base solution is Na with different concentrations2CO3Ammonium carbonate, ammonia water, K2CO3、NaHCO3、KHCO3、NH4HCO3One or a mixture of two or more of them, V is the effective volume L of the reactor, c is iron-containing solutionThe iron content in the liquid is g/L.
2. The method for removing iron from an iron-containing solution according to claim 1, wherein: in the step (1), the iron-containing solution is firstly oxidized by air and then deeply oxidized by an oxidant, or is directly oxidized by the oxidant.
3. The method for removing iron from an iron-containing solution according to claim 2, wherein: the oxidant is H2O2、Cl2、KClO3、NaClO、NaClO3One of them.
4. The method for removing iron from an iron-containing solution according to claim 1, wherein: the amount of the iron yellow seed solution added in the step (3) is 1/4 of the effective volume of the reactor.
5. The method for removing iron from an iron-containing solution according to claim 1, wherein: the value of the dripping speed L/min of the iron-containing solution in the step (3) is V/15 c-V/8 c.
6. The method for removing iron from an iron-containing solution according to claim 1, wherein: the stirring speed in the step (3) is 60 r/min.
7. The method for removing iron from an iron-containing solution according to claim 1, wherein: and (3) after the volume of the reaction liquid reaches the effective volume of the reactor, starting to extract the reaction liquid from the bottom of the reactor, and continuing to simultaneously dropwise add the iron-containing solution and the weak base solution, wherein the extracted volume of the reaction liquid is equal to the sum of the dropwise added volumes of the iron-containing solution and the weak base solution.
8. The method for removing iron from an iron-containing solution according to claim 1, wherein: and (3) stopping dropwise adding the weak base solution and the iron-containing solution after the volume of the reaction solution reaches the effective volume of the reactor in the step (3), continuing stirring for 5-10 minutes, standing and settling for 10-15 minutes, extracting 3/4 reaction solution with the effective volume of the reactor from the reactor, and filtering to obtain the iron-removing solution.
9. The method for removing iron from an iron-containing solution according to claim 1, wherein the method for preparing the iron oxide yellow seed crystal comprises: firstly, mixing a mixed solution of ethylenediamine tetraacetic acid, copperas and water according to the weight ratio of 2: 50-100: 1000, and stirring until the copperas are completely dissolved; then, 2-4mol/L ammonia water or Na with the concentration of 10-15 percent is added dropwise2CO3Dropwise adding the solution at the speed of 1-4L/hour/20L of copperas solution until the pH value of the solution is equal to 8.2-8.7, and stopping dropwise adding ammonia water; and after continuously stirring for 10-20 minutes, starting introducing oxygen for oxidation, continuously dropwise adding ammonia water until the pH value is reduced to 4 and stabilized, adjusting the pH value to 5, stopping dropwise adding ammonia water, gradually reducing and stabilizing the pH value along with the progress of oxidation reaction, dropwise adding ammonia water for a period of time, gradually increasing the pH value to 7, stabilizing the pH value at the moment, stopping dropwise adding ammonia water without reducing along with the extension of reaction time, continuously stirring for 15-20 minutes, stopping introducing oxygen, standing and aging for 1 hour, and filtering to obtain the r-type iron yellow crystal seed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100331052A CN100357192C (en) | 2006-01-16 | 2006-01-16 | Deferrization method of iron-containing liquor |
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| CN102807278A (en) * | 2012-08-07 | 2012-12-05 | 华南理工大学 | Method for removing irons from alkaline etching liquid waste of printed-circuit boards |
| CN102897824B (en) * | 2012-10-30 | 2015-08-12 | 广州汉源新材料有限公司 | A kind of technique of copper sulfate deironing |
| CN104030510B (en) * | 2014-06-10 | 2016-03-02 | 安可珍 | A kind of method of acid and heavy metal recovery in gold smelting acid waste water |
| CN106191463B (en) * | 2016-07-15 | 2018-10-16 | 深圳市深投环保科技有限公司 | A kind of purification method of zinc hydrometallurgy leachate |
| CN113171584B (en) * | 2021-04-26 | 2022-07-01 | 天津海成能源工程技术有限公司 | Iron removing liquid and method for removing iron ions of high-boiling residues of VCM device |
| CN113603148A (en) * | 2021-07-13 | 2021-11-05 | 斯瑞尔环境科技股份有限公司 | Resource utilization method for fractional precipitation separation of high-content zinc and iron waste acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104992A (en) * | 1994-07-08 | 1995-07-12 | 山东新华制药厂 | Method for treating ferrous salt in industrial halogen hydrogen acid |
| CN1223963A (en) * | 1998-12-14 | 1999-07-28 | 华南理工大学 | Method for removing iron ions from soda lye |
| US6800260B2 (en) * | 2002-02-11 | 2004-10-05 | Millennium Inorganic Chemicals, Inc. | Processes for treating iron-containing waste streams |
| JP2005008455A (en) * | 2003-06-17 | 2005-01-13 | Japan Nuclear Cycle Development Inst States Of Projects | Method for separating and recovering iron and manganese which coexist in water |
-
2006
- 2006-01-16 CN CNB2006100331052A patent/CN100357192C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104992A (en) * | 1994-07-08 | 1995-07-12 | 山东新华制药厂 | Method for treating ferrous salt in industrial halogen hydrogen acid |
| CN1223963A (en) * | 1998-12-14 | 1999-07-28 | 华南理工大学 | Method for removing iron ions from soda lye |
| US6800260B2 (en) * | 2002-02-11 | 2004-10-05 | Millennium Inorganic Chemicals, Inc. | Processes for treating iron-containing waste streams |
| JP2005008455A (en) * | 2003-06-17 | 2005-01-13 | Japan Nuclear Cycle Development Inst States Of Projects | Method for separating and recovering iron and manganese which coexist in water |
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