CN101348282A - Method for deeply purifying and removing titanium in copperas solution - Google Patents
Method for deeply purifying and removing titanium in copperas solution Download PDFInfo
- Publication number
- CN101348282A CN101348282A CNA2008101431080A CN200810143108A CN101348282A CN 101348282 A CN101348282 A CN 101348282A CN A2008101431080 A CNA2008101431080 A CN A2008101431080A CN 200810143108 A CN200810143108 A CN 200810143108A CN 101348282 A CN101348282 A CN 101348282A
- Authority
- CN
- China
- Prior art keywords
- solution
- ferrous sulfate
- titanium
- add
- reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a method for deep purifying and titanium removal in a ferrous sulfate solution. The method comprises the following: a step of dissolving, which is to dissolve ferrous sulfate that is a byproduct of titanium dioxide production in deionized water, keep stand, extract supernatant for standby, press-filter and discard dissolution slag; a step of reducing, which is to add 1 to 2 percent of reduction iron powder to the supernatant at a temperature between 25 and 35 DEG C until the solution turns blue; and a step of neutralizing, which is to add ferrous oxide powder to the reduced ferrous sulfate solution to regulate the pH of the solution to between 1 and 5, stir the solution for 30 to 90 minutes until the solution turns bright green, filter and obtain pure ferrous sulfate solution. The method is high in titanium removal rate, little in iron loss and stable in technical process, obtains the pure ferrous sulfate solution without introducing other metal impurities, can judge reaction end points through the color of the solution before and after reduction, and is simple in process control, low in operation temperature, short in treatment time and low in comprehensive cost.
Description
Technical field
The present invention relates to hydrometallurgy process in the field of metallurgy, particularly the method for deeply purifying and removing titanium from copperas solution effectively.
Background technology
The sulfuric acid process preparation technology of titanium dioxide leaches ilmenite with sulfuric acid, make titanium and iron all enter solution, after sedimentation removal impurity, subzero fractionation go out by-product ferrous sulfate during, add crystal seed and make titanyl sulfate be hydrolyzed to metatitanic acid, after 800～1000 ℃ of calcinings, pulverizing, obtain titanium dioxide through the washing back.By-product ferrous sulfate during (the FeSO that this technological process produces
47H
2O) classical composition is (%): FeSO
485.0, TiO
20.8, developed multiple use: can prepare the technical grade ferrous sulfate, products such as inorganic macromolecule flocculant poly ferric sulfate, iron oxide yellow or red iron oxide, Ferrox and ferric lithium phosphate precursor are arranged; If this by product directly is used for producing the compound of high-quality iron, wherein the content of titanium is higher, influences quality product, so need the titanium in the deep purifying copperas solution.
The method of titanium is with after the dissolving of this by-product ferrous sulfate during in traditional cleansing soln, and directly with the residual acid in ammoniacal liquor or the dilute alkaline soln neutralisation of sulphuric acid ferrous iron solution, the pH of regulator solution＞1.5 are lower than in temperature under 60 ℃ the condition, generate coarse grained metatitanic acid H
2TiO
3, the copperas solution of the titanium that is removed after the filtration, as the method for Chinese patent CN100357361C introduction, but the titanium content in the solution of in these class methods and back is still at 200～400mgL
-1Between, can not satisfy the requirement of high-quality product, and this treating processes being difficult to effective control, titanium content residual in the solution alters a great deal.
There is following shortcoming in the method for removing titanium in the above-mentioned copperas solution:
(1) quaternary titanium hydrolysis degree is incomplete, and titanium content is at 200～400mgL in the solution of precipitation end back
-1Between;
(2) owing to ferric existence, directly the solution behind the neutralization precipitation is difficult to filter;
(3) reaction end is difficult to accurate judgement.
Summary of the invention
In order to overcome the deficiency of traditional copperas solution purifying and removing titanium method, the invention provides titanium in a kind of copperas solution of deep purifying effectively, and process Wet-process metallurgy method efficiently.
For achieving the above object, the present invention utilizes lower valency hydrolytic precipitation principle more completely in solution, with the by-product ferrous sulfate during of producing in the titanium dioxide process, after water dissolution, add iron powder again the titanium in the solution is reduced to lower valency, after reaction for some time, the pH that adds the ferrous oxide powder regulator solution makes the titanium hydrolytic precipitation of lower valency, react the after-filtration that finishes, the purified copperas solution of output.
Concrete technological process and processing parameter are as follows:
1 dissolving
With the by-product ferrous sulfate during of producing titanium dioxide according to liquid-solid ratio 1.5～3: 1 is dissolved in the deionized water, and leaving standstill the back, to extract supernatant liquor out stand-by, discarded after the press filtration of dissolving slag;
2 reduction
In the time of 25～35 ℃, in supernatant liquor, add 1～2% reduced iron powder, low whipping speed 150～300rmin
-1Under react 30～120min, solution becomes blueness and is terminal point.The chemical reaction that reduction process takes place is:
Fe+2Fe
3+＝3Fe
2+ (1)
Fe+2TiO
2++4H
++H
2O＝Fe
2++2Ti(H
2O)
3 3+ (2)
3 neutralizations
PH=1～5 that add the ferrous powder regulator solution of small amounts in the copperas solution after reduction are stirred behind 30～90min solution and are become bright green and be terminal point, filter and obtain purified copperas solution, and the chemical reaction that N-process takes place is:
2Ti(H
2O)
3 3++3FeO＝2Ti(OH)
3↓+3Fe
2++3H
2O (3)
Described iron powder, ferrous oxide powder are technical grade reagent.
The present invention is applicable to the titanium impurity in the deep purifying copperas solution, and wherein the content range of titanium is: 0.006～20gL
-1Also be suitable for handling the purification of titanium in other sulfate liquors.
The present invention and traditional copperas solution purifying and removing titanium technical process comparison, following advantage is arranged: the present invention is the decreasing ratio height of titanium not only, and the loss of iron is little, stable technical process; Do not introduce other metallic impurity when removing the titanium ion in the copperas solution, obtain purified copperas solution; This technological process can be judged reaction end by the color before and after the solution reduction, and process control is simple; Service temperature is low, the treatment time is short, comprehensive cost is low.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Embodiment:
Embodiment 1: add the 75L pure water in reactor, add 50Kg technical grade ferrous sulfate then, behind the standing demix of stirring 30min dissolving back, filtering supernatant obtains titaniferous 2.2gL
-1Copperas solution, take by weighing the 500g iron powder and add wherein, solution became blueness after normal temperature stirred 2h down, detecting with potassium sulfocyanate does not have ferric iron to exist; Add the 250g ferrous oxide powder and regulate molten pH=4.00, solution is greyish-green, continues to stir the 1h after-filtration, purifies slag and reclaims the iron powder that does not participate in reaction through magnetic separation, and titanium content is 0.09mgL in the copperas solution after the purification
-1
Embodiment 2: add the 1500L pure water in reactor, add 1000Kg technical grade ferrous sulfate then, behind the standing demix of stirring 30min dissolving back, filtering supernatant obtains titaniferous 2.5gL
-1Copperas solution, take by weighing the 10Kg iron powder and add wherein, solution became blueness after normal temperature stirred 2h down, detecting with potassium sulfocyanate does not have ferric iron to exist; Add 5Kg ferrous oxide powder regulator solution pH=4.20, solution is greyish-green, continues to stir the 1h after-filtration, purifies slag and reclaims the iron powder that does not participate in reaction, titanium content 0.08mgL in the copperas solution after the purification through magnetic separation
-1
Claims (2)
1. the method for deeply purifying and removing titanium in the copperas solution is characterized in that comprising the following steps:
(1) dissolving
With the by-product ferrous sulfate during of producing titanium dioxide according to liquid-solid ratio 1.5～3: 1 is dissolved in the deionized water, and leaving standstill the back, to extract supernatant liquor out stand-by, discarded after the press filtration of dissolving slag;
(2) reduction
In the time of 25～35 ℃, in supernatant liquor, add 1～2% reduced iron powder, low whipping speed 150～300rmin
-1Under react 30～120min, solution becomes blueness and is terminal point, the chemical reaction that reduction process takes place is:
Fe+2Fe
3+＝3Fe
2+ (1)
Fe+2TiO
2++4H
++H
2O＝Fe
2++2Ti(H
2O)
3 3+ (2)
(3) neutralization
PH=1～5 that add iron protoxide powder regulator solution in the copperas solution after reduction are stirred behind 30～90min solution and are become bright green and be terminal point, filter and obtain purified copperas solution, and the chemical reaction that N-process takes place is:
2Ti(H
2O)
3 3++3FeO＝2Ti(OH)
3↓+3Fe
2++3H
2O (3)
2. the method for deeply purifying and removing titanium in the copperas solution according to claim 1 is characterized in that: described iron powder, ferrous oxide powder are technical grade reagent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810143108A CN100591622C (en) | 2008-09-01 | 2008-09-01 | Method for deeply purifying and removing titanium in copperas solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810143108A CN100591622C (en) | 2008-09-01 | 2008-09-01 | Method for deeply purifying and removing titanium in copperas solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101348282A true CN101348282A (en) | 2009-01-21 |
| CN100591622C CN100591622C (en) | 2010-02-24 |
Family
ID=40267282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810143108A Expired - Fee Related CN100591622C (en) | 2008-09-01 | 2008-09-01 | Method for deeply purifying and removing titanium in copperas solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100591622C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948379A (en) * | 2010-09-01 | 2011-01-19 | 中国科学院宁波材料技术与工程研究所 | Method for preparing battery-level ferrous oxalate |
| CN108455547A (en) * | 2018-02-11 | 2018-08-28 | 衢州华友钴新材料有限公司 | A kind of low impurity high ferro phosphorus is than greatly than the preparation method of table battery-grade iron phosphate |
| CN113968578A (en) * | 2021-12-06 | 2022-01-25 | 紫金矿业集团股份有限公司 | Method for synthesizing iron phosphate by using ferrous sulfate as titanium dioxide byproduct |
| CN114162875A (en) * | 2021-12-31 | 2022-03-11 | 龙佰集团股份有限公司 | Preparation method and preparation device of ferrous sulfate solution for iron oxide pigment and iron oxide pigment |
| CN115382444A (en) * | 2022-10-27 | 2022-11-25 | 山东彩客新材料有限公司 | Ferrous sulfate purification device and method |
| CN116239145A (en) * | 2023-03-24 | 2023-06-09 | 甘肃佰利联化学有限公司 | Method for co-production and recovery of titanium by iron phosphate-titanium |
-
2008
- 2008-09-01 CN CN200810143108A patent/CN100591622C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948379A (en) * | 2010-09-01 | 2011-01-19 | 中国科学院宁波材料技术与工程研究所 | Method for preparing battery-level ferrous oxalate |
| CN101948379B (en) * | 2010-09-01 | 2013-04-10 | 中国科学院宁波材料技术与工程研究所 | Method for preparing battery-level ferrous oxalate |
| CN108455547A (en) * | 2018-02-11 | 2018-08-28 | 衢州华友钴新材料有限公司 | A kind of low impurity high ferro phosphorus is than greatly than the preparation method of table battery-grade iron phosphate |
| CN108455547B (en) * | 2018-02-11 | 2019-09-03 | 衢州华友钴新材料有限公司 | A kind of preparation method of low impurity high-speed rail phosphorus than bigger serface battery-grade iron phosphate |
| CN113968578A (en) * | 2021-12-06 | 2022-01-25 | 紫金矿业集团股份有限公司 | Method for synthesizing iron phosphate by using ferrous sulfate as titanium dioxide byproduct |
| CN114162875A (en) * | 2021-12-31 | 2022-03-11 | 龙佰集团股份有限公司 | Preparation method and preparation device of ferrous sulfate solution for iron oxide pigment and iron oxide pigment |
| CN115382444A (en) * | 2022-10-27 | 2022-11-25 | 山东彩客新材料有限公司 | Ferrous sulfate purification device and method |
| CN116239145A (en) * | 2023-03-24 | 2023-06-09 | 甘肃佰利联化学有限公司 | Method for co-production and recovery of titanium by iron phosphate-titanium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100591622C (en) | 2010-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2743355C1 (en) | Method of extracting vanadium from vanadium slag with high content of calcium and phosphorus | |
| CN100591622C (en) | Method for deeply purifying and removing titanium in copperas solution | |
| RU2736539C1 (en) | Method of producing vanadium oxide of a battery grade | |
| CN102181635A (en) | Method for preparing vanadium pentoxide from stone coal vanadium ore sulfuric acid leaching solution | |
| AU598671B2 (en) | Process for the recovery of germanium from solutions that contain it | |
| CN102828025A (en) | Method for extracting V2O5 from stone coal navajoite | |
| CN104726724A (en) | Method for extracting scandium from nickel laterite ores | |
| CN110760687A (en) | Method for cleanly extracting vanadium from low-cost vanadium slag | |
| CN105734283B (en) | A kind of method that Zn, Cu, Ge, Ga are extracted from containing Zn, Cu, Ge, Ga, Fe material | |
| CN110983044B (en) | Method for recycling scandium and vanadium from titanium white wastewater produced by chlorination process | |
| US10724119B2 (en) | Process for the separation of vanadium | |
| CN102167400A (en) | Method for preparing vanadium pentoxide from vanadium-containing solution | |
| CA1079488A (en) | Treatment method of raw materials containing titanium | |
| CN102888512A (en) | Impurity removing method of vanadium solution | |
| CN104609472B (en) | A kind of titanium tetrachloride refines the method except vanadium mud produces vanadic anhydride | |
| CN113186395A (en) | Method for preparing vanadyl sulfate from vanadium-containing solution | |
| CN106367606A (en) | Method for separating and recovering chromium from vanadium-chromium waste residues | |
| CN104060093B (en) | A kind for the treatment of process of waste water neutralize gypsum tailings | |
| CN112301220A (en) | Method for reducing iron content in rare earth sulfate water leaching solution | |
| CN104862503A (en) | Method for extracting scandium from nickel laterite ore | |
| CN114672668B (en) | Method for preparing vanadium pentoxide by reducing precipitated vanadium and vanadium pentoxide and application | |
| CN108893613B (en) | Zinc oxide powder zinc galvanizing process | |
| CN114350981A (en) | Method for recovering vanadium from calcified vanadium extraction tailings | |
| CN111020233A (en) | Method for preparing vanadium pentoxide by ammonium-free vanadium precipitation | |
| CN110550664B (en) | Method for preparing iron oxide red by roasting cyanide tailings containing arsenic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGXI LONGTIANYONG NONFERROUS METAL CO., LTD. Free format text: FORMER OWNER: LIU WEIFENG Effective date: 20120119 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 410083 CHANGSHA, HUNAN PROVINCE TO: 331500 JI'AN, JIANGXI PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20120119 Address after: 331500 Yongfeng Industrial Park, Jiangxi, Ji'an Patentee after: JIANGXI LONGTIANONG NONFERROUS METAL CO.,LTD. Address before: 410083 School of metallurgy, Central South University, Hunan 101, Changsha Province Patentee before: Liu Weifeng |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100224 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |