CN106082324A - A kind of iron-free Zr (SO4)2production method - Google Patents
A kind of iron-free Zr (SO4)2production method Download PDFInfo
- Publication number
- CN106082324A CN106082324A CN201610390117.4A CN201610390117A CN106082324A CN 106082324 A CN106082324 A CN 106082324A CN 201610390117 A CN201610390117 A CN 201610390117A CN 106082324 A CN106082324 A CN 106082324A
- Authority
- CN
- China
- Prior art keywords
- solution
- iron
- free
- longer
- production method
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/06—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of iron-free Zr (SO4)2Production method, comprise the following steps: a, be placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and in container, drip organic reducing agent solution, until no longer there being ferric ion to detect；Regulate to 3～5 by the pH value of ammonia spirit regulation solution again；B, be stirred continuously and in through the reacted solution of step a drip Phen solution, until no longer there being ferrous ion to detect, soluble chloride solution or sodium picrate solution is constantly dripped again in container, until no longer there being precipitation to generate, after carrying out separation of solid and liquid, gained liquid is iron-free Zr (SO4)2Solution.The invention has the beneficial effects as follows: the original technological process of production need not be changed；Iron separates completely；Product purity is high；Produce without discarded object；Precipitating reagent can be with recycling, and production cost is low；Precipitating reagent agent is selectively high, and product loss is little；Do not produce Zr (OH) in acid condition4Precipitation.
Description
Technical field
The present invention relates to the production method of a kind of zirconium sulfate, especially a kind of iron-free Zr (SO4)2Production method.
Background technology
The technique of industrial production zirconium sulfate mainly has: one is that zircon soaks through washing, sulfuric acid through oversintering or alkali fusion
Go out, ammonia precipitation process, washing except sodium, sulfuric acid dissolution, evaporative crystallization, be recrystallized to give zirconium sulfate product.Another kind is zircon warp
Cross alkali fusion, washing, salt Ore Leaching, hydrolysis, sulfuric acid dissolution, crystallization obtain zirconium sulfate product.Above two production technology will be through
Overpickling, the metal impurities iron in raw material and acid are reacted in zirconium sulfate solution, affect the quality of product.Industry removes Tie Tong
Often add oxidant after pickling, by Fe2+It is oxidized to Fe3+, regulate solution acidity Fe3+Generate Fe (OH)3Precipitate and separate.This
Separate Fe3+Method is incomplete, Fe (OH)3Filtration difficulty, and a part of Zr (SO4)2Also Zr (OH) can be generated4Precipitation causes damage
Lose.Or use salt adding acid except the method for iron, in one time of crystallization, i.e. add a certain amount of hydrochloric acid, make iron be formed
[FeCl4]-Not forming eutectic and minimizing with zirconium sulfate and being reached de-ferrous effect by zirconium sulfate absorption, this method equipment corrosion is serious.
Therefore, ferro element can either be separated completely by one, again the iron-free Zr (SO of not etching apparatus4)2Production method become
For solving the key of problem.
Content of the invention
As the result of various extensive and careful researchs and experiment, present inventors have found that: by zirconium sulfate
Fe in solution3+It is reduced to Fe2+, prepare the Zr (SO of iron-free4)2, ferro element can be separated completely, again not etching apparatus.
One object of the present invention provides a kind of iron-free Zr (SO4)2Production method, ferro element can either be separated completely,
Not etching apparatus again.
For achieving the above object, the present invention provides a kind of iron-free Zr (SO4)2Production method, comprise the steps:
It a, is placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and to container
Middle dropping organic reducing agent solution, until no longer there being ferric ion to detect；PH value regulation with ammonia spirit regulation solution again
To 3～5；
B, be stirred continuously and in through the reacted solution of step a drip Phen solution, until no longer there being ferrous iron
Ion detects, more constantly dropping soluble chloride solution or sodium picrate solution in container, until no longer there being precipitation to generate,
After carrying out separation of solid and liquid, gained liquid is iron-free Zr (SO4)2Solution.
Preferably, the organic reducing agent described in step a is any one in hydroxylamine hydrochloride or ascorbic acid.
Preferably, the organic reducing agent described in step a is hydroxylamine hydrochloride.
Preferably, in step a, the mass fraction of ammonia spirit is 25%～28%.
Preferably, the mass fraction of Phen solution described in step b is 5-10%.
Preferably, soluble chloride described in step b is any one in sodium chloride, calcium chloride or potassium chloride.
Preferably, it is placed in the solid that 1 weight portion obtains after separation of solid and liquid in step b in container, then add 2.95～
The water of 3.05 weight portions, at 75～80 DEG C, then the NaOH that the mass fraction dripping 2.6～2.8 mass parts is 10% is molten
Liquid, reacts 25～30min, after separation of solid and liquid, it is thus achieved that C12H8N2Solution.
Preferably, in step a, in zirconium sulfate solution, drip potassium thiocyanate solution no longer show redness or to sulfuric acid
Zirconium solution drips potassium ferrocyanide solution and no longer shows blueness, be considered as no longer having ferric ion to detect.
Preferably, in stepb, dripping the potassium ferricyanide in solution no longer has blue precipitate to generate, and is considered as no longer having
Ferrous ion detects.
Preferably, the mass fraction of hydroxylamine hydrochloride solution is 10-20%.
The invention has the beneficial effects as follows: the original technological process of production need not be changed；Iron separates completely；Product purity is high；Nothing
Discarded object produces；Precipitating reagent can be with recycling, and production cost is low；Precipitating reagent agent is selectively high, and product loss is little；In acidity
Under the conditions of do not produce Zr (OH)4Precipitation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, to make those skilled in the art's reference say
Bright book word can be implemented according to this.
Embodiment 1
It a, is placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and to container
Middle dropping mass fraction is the hydroxylamine hydrochloride solution of 15%, when in zirconium sulfate solution, dropping potassium thiocyanate solution no longer shows redness
When, it is considered as no longer having ferric ion to detect；Regulate extremely by the pH value of the ammonia spirit regulation solution that mass fraction is 26% again
4；In the process, there is following chemical equation:
2Fe3++2NH2OH HCl=2Fe2++N2↑+4H++2H2O+2Cl-
B, be stirred continuously and in through the reacted solution of step a drip mass fraction be 8% Phen solution, to
In solution, the dropping potassium ferricyanide is when no longer there being blue precipitate to generate, and is considered as no longer having ferrous ion to detect.Again in container
Constantly dropping mass fraction is the sodium chloride solution of 35%, until no longer there being precipitation to generate, after filtering, gained liquid is
Iron-free Zr (SO4)2Solution；In the process, there is following chemical equation:
Fe2++3C12H8N2=[Fe (C12H8N2)3]2+
[Fe(C12H8N2)3]2++2Cl-=[Fe (C12H8N2)3]Cl2↓
C, will through step b reaction solid be placed in vessel, add solid masses 3 times water, at 78 DEG C, drip solid matter
Measuring the sodium hydroxide solution that the mass fraction of 2.7 times is 10%, reacting 27min, after filtration, gained filtrate is C12H8N2Solution.
Embodiment 2
It a, is placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and to container
Middle dropping mass fraction is the hydroxylamine hydrochloride solution of 10%, when in zirconium sulfate solution, dropping potassium thiocyanate solution no longer shows redness
When, it is considered as no longer having ferric ion to detect；Regulate extremely by the pH value of the ammonia spirit regulation solution that mass fraction is 25% again
5；
B, be stirred continuously and in through the reacted solution of step a drip mass fraction be 5% Phen solution, to
In solution, the dropping potassium ferricyanide is when no longer there being blue precipitate to generate, and is considered as no longer having ferrous ion to detect.Again in container
Constantly dropping mass fraction is the calcium chloride solution of 30%, until no longer there being precipitation to generate, after filtering, gained liquid is
Iron-free Zr (SO4)2Solution；
C, will be placed in vessel through step b reaction solid, and add the water of solid masses 2.95 times, at 80 DEG C, dropping is solid
The mass fraction that weight is 2.6 times is the sodium hydroxide solution of 10%, reacts 30min, and after filtration, gained filtrate is C12H8N2
Solution.
Embodiment 3
It a, is placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and to container
Middle dropping mass fraction is the hydroxylamine hydrochloride solution of 20%, when in zirconium sulfate solution, dropping potassium thiocyanate solution no longer shows redness
When, it is considered as no longer having ferric ion to detect；Regulate extremely by the pH value of the ammonia spirit regulation solution that mass fraction is 28% again
3；
B, be stirred continuously and in through the reacted solution of step a drip mass fraction be 10% Phen solution,
In solution, the dropping potassium ferricyanide is when no longer there being blue precipitate to generate, and is considered as no longer having ferrous ion to detect.Again to container
Interior constantly dropping mass fraction is the Klorvess Liquid of 40%, until no longer there being precipitation to generate, after filtering, gained liquid is
For iron-free Zr (SO4)2Solution；
C, will be placed in vessel through step b reaction solid, and add the water of solid masses 3.05 times, at 75 DEG C, dropping is solid
The mass fraction that weight is 2.8 times is the sodium hydroxide solution of 10%, reacts 25min, and after filtration, gained filtrate is C12H8N2
Solution.
Embodiment 4
It a, is placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and to container
Middle dropping mass fraction is the ascorbic acid solution of 18%, when in zirconium sulfate solution, dropping potassium ferrocyanide solution no longer shows indigo plant
It during look, is considered as no longer having ferric ion to detect；PH value regulation with the ammonia spirit regulation solution that mass fraction is 26% again
To 4.5；
B, be stirred continuously and in through the reacted solution of step a drip mass fraction be 6% Phen solution, to
In solution, the dropping potassium ferricyanide is when no longer there being blue precipitate to generate, and is considered as no longer having ferrous ion to detect.Again in container
Constantly dropping mass fraction is the sodium picrate solution of 38%, until no longer there being precipitation to generate, after filtering, gained liquid is
For iron-free Zr (SO4)2Solution；
C, will be placed in vessel through step b reaction solid, and add the water of solid masses 3.02 times, at 76 DEG C, dropping is solid
The mass fraction that weight is 2.75 times is the sodium hydroxide solution of 10%, reacts 26min, and after filtration, gained filtrate is C12H8N2
Solution.
Embodiment 5
It a, is placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and to container
Middle dropping mass fraction is the ascorbic acid solution of 12%, when in zirconium sulfate solution, dropping potassium ferrocyanide solution no longer shows indigo plant
It during look, is considered as no longer having ferric ion to detect；PH value regulation with the ammonia spirit regulation solution that mass fraction is 26% again
To 3.5；
B, be stirred continuously and in through the reacted solution of step a drip mass fraction be 9% Phen solution, to
In solution, the dropping potassium ferricyanide is when no longer there being blue precipitate to generate, and is considered as no longer having ferrous ion to detect.Again in container
Constantly dropping mass fraction is the sodium chloride solution of 32%, until no longer there being precipitation to generate, after filtering, gained liquid is
Iron-free Zr (SO4)2Solution；
C, will be placed in vessel through step b reaction solid, and add the water of solid masses 2.97 times, at 79 DEG C, dropping is solid
The mass fraction that weight is 2.65 times is the sodium hydroxide solution of 10%, reacts 29min, and after filtration, gained filtrate is C12H8N2
Solution.
Comparative example 1
It a, is placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and to container
Middle dropping mass fraction is the hydroxylamine hydrochloride solution of 30%；PH value with the ammonia spirit regulation solution that mass fraction is 20% again
Regulation is to 2；
B, be stirred continuously and in through the reacted solution of step a drip mass fraction be 4% Phen solution.Again
In container, constantly dropping mass fraction is the sodium chloride solution of 45%, until no longer there being precipitation to generate, after filtering, and gained
Liquid is iron-free Zr (SO4)2Solution.
Comparative example 2
It a, is placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and to container
Middle dropping mass fraction is the hydroxylamine hydrochloride solution of 8%；PH value with the ammonia spirit regulation solution that mass fraction is 30% again
Regulation is to 6；
B, be stirred continuously and in through the reacted solution of step a drip mass fraction be 12% Phen solution.
In container, constantly dropping mass fraction is the sodium chloride solution of 25% again, until no longer there being precipitation to generate, after filtering, and institute
Obtain liquid and be iron-free Zr (SO4)2Solution.
Measure the iron-free Zr (SO being prepared by embodiment 1～5 and comparative example 1～2 respectively4)2Iron content in solution.Gained
The results are shown in Table one.
Table one
| Project | Zr(SO<sub>4</sub>)<sub>2</sub>Middle iron content/ppm |
| Embodiment 1 | 30 |
| Embodiment 2 | 32 |
| Embodiment 3 | 34 |
| Embodiment 4 | 29 |
| Embodiment 5 | 31 |
| Comparative example 1 | 81 |
| Comparative example 2 | 54 |
By table one it can be seen that the iron-free Zr (SO preparing according to the method for the present invention4)2Iron content in solution is substantially little
In comparative example 1 and comparative example 2.
Data analysis
(1)C12H8N2The impact on iron separating effect for the addition
Weigh 100gZr (SO4)2Solution (iron content is 0.72%) is placed in the container of 1000mL, at normal temperatures and pressures, adds
Enter different amounts of C12H8N2Solution, is adding sodium chloride to occurring without precipitation.It is stirred continuously solution simultaneously, after reaction 30min, mistake
The precipitation that filter generates, the Zr (SO obtaining4)2Middle iron content is less than 30ppm.The data obtained is shown in Table two.
Table two C12H8N2The impact on de-ferrous effect for the addition
As shown in Table 2, with C12H8N2The separation of the increase of addition, beneficially iron, but work as C12H8N2The increasing of addition
After being added to determine degree, separate the DeGrain of iron.Work as C12H8N2With the amount of the material of iron than for best results during 3:1.
(2)Zr(SO4)2The impact on de-ferrous effect for the acidity of solution
Under identical condition, the acid-base value of solution is changed.The impact on de-ferrous effect for the solution acid alkalinity, the data obtained is shown in
Table three.
The impact on de-ferrous effect for table three acidity
| Sequence number | 1 | 2 | 3 | 4 | 5 | 6 |
| PH value of solution | 0.5 | 1 | 1.5 | 2.0 | 2.5 | 3.0 |
| Iron content/ppm | 81 | 55 | 40 | 35 | 30 | 29 |
As shown in Table 3, the higher de-ferrous effect of the pH of solution is better, but pH is more high easily causes Zr (SO4)2Precipitation.Select
PH=3-5.
The production method of a kind of iron-free Zr (SO4) 2 of the present invention described above, need not change the original technological process of production；Iron
Separate completely；Product purity is high；Produce without discarded object；Precipitating reagent can be with recycling, and production cost is low；Precipitating reagent agent selects
Property high, product loss is little；Do not produce Zr (OH) in acid condition4Precipitation.
Although embodiment of the present invention are disclosed as above, but it is not restricted to listed fortune in bright book and embodiment
With, it can be applied to various applicable the field of the invention completely, for those skilled in the art, and can be easily real
Now other modification, therefore under the universal being limited without departing substantially from claim and equivalency range, the present invention is not limited to
Specific details.
Claims (10)
1. an iron-free Zr (SO4)2Production method, it is characterised in that comprise the steps:
It a, is placed in the zirconium sulfate solution containing ferrous ion and ferric ion in container, be stirred continuously and drip in container
Added with machine reductant solution, until no longer there being ferric ion to detect；Again with the pH value regulation of ammonia spirit regulation solution to 3～
5；
B, be stirred continuously and in through the reacted solution of step a drip Phen solution, until no longer there being ferrous ion
Detection, more constantly dropping soluble chloride solution or sodium picrate solution in container, until no longer there being precipitation to generate, carried out
After separation of solid and liquid, gained liquid is iron-free Zr (SO4)2Solution.
2. iron-free Zr (SO as claimed in claim 14)2Production method, it is characterised in that: the organic reducing described in step a
Agent is any one in hydroxylamine hydrochloride or ascorbic acid.
3. iron-free Zr (SO as claimed in claim 24)2Production method, it is characterised in that: the organic reducing described in step a
Agent is hydroxylamine hydrochloride.
4. iron-free Zr (SO as claimed in claim 1 or 24)2Production method, it is characterised in that: ammonia spirit in step a
Mass fraction is 25%～28%.
5. iron-free Zr (SO as claimed in claim 1 or 24)2Production method, it is characterised in that: adjacent Féraud described in step b
The mass fraction of quinoline solution is 5-10%.
6. iron-free Zr (SO as claimed in claim 14)2Production method, it is characterised in that: solubility chlorination described in step b
Thing is any one in sodium chloride, calcium chloride or potassium chloride.
7. iron-free Zr (SO as claimed in claim 14)2Production method, it is characterised in that: by 1 weight portion through solid in step b
The solid that liquid obtains after separating is placed in container, adds the water of 2.95～3.05 weight portions, at 75～80 DEG C, then drips
The mass fraction of 2.6～2.8 mass parts is the sodium hydroxide solution of 10%, reacts 25～30min, after separation of solid and liquid, it is thus achieved that
C12H8N2Solution.
8. iron-free Zr (SO as claimed in claim 14)2Production method, it is characterised in that: in step a, molten to zirconium sulfate
Liquid drips potassium thiocyanate solution no longer show red or in zirconium sulfate solution, drip the no longer aobvious blueness of potassium ferrocyanide solution,
It is considered as no longer having ferric ion to detect.
9. iron-free Zr (SO as claimed in claim 14)2Production method, it is characterised in that: in stepb, in solution drip
Adding the potassium ferricyanide no longer has blue precipitate to generate, and is considered as no longer having ferrous ion to detect.
10. iron-free Zr (SO as claimed in claim 34)2Production method, it is characterised in that: the quality of hydroxylamine hydrochloride solution is divided
Number is 10-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610390117.4A CN106082324B (en) | 2016-06-03 | 2016-06-03 | A kind of iron-free Zr (SO4)2Production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610390117.4A CN106082324B (en) | 2016-06-03 | 2016-06-03 | A kind of iron-free Zr (SO4)2Production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106082324A true CN106082324A (en) | 2016-11-09 |
| CN106082324B CN106082324B (en) | 2018-03-06 |
Family
ID=57447702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610390117.4A Active CN106082324B (en) | 2016-06-03 | 2016-06-03 | A kind of iron-free Zr (SO4)2Production method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106082324B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100207A (en) * | 1987-01-07 | 1988-07-20 | 上海跃新化工厂 | Produce zirconium white by zircon |
| CN1125195A (en) * | 1994-12-18 | 1996-06-26 | 常正亚 | Producing zirconium series products using non-crystallization purification method |
-
2016
- 2016-06-03 CN CN201610390117.4A patent/CN106082324B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87100207A (en) * | 1987-01-07 | 1988-07-20 | 上海跃新化工厂 | Produce zirconium white by zircon |
| CN1125195A (en) * | 1994-12-18 | 1996-06-26 | 常正亚 | Producing zirconium series products using non-crystallization purification method |
Non-Patent Citations (2)
| Title |
|---|
| YUROKU YAMAMOTO ET AL.: ""CONDUCTANCE OF TRIS( l,lO-PHENANTHROLINE)IRON(II) AND TRIS(2,2’-BIPYRIDINE)IRON(II) HALIDES AND PERCHLORATES IN WATER AND NITROBENZENE IN RELATION TO SOLVENT EXTRACTION OF THE ION PAIRS"", 《ANALYTICA CHIMICA ACTA》 * |
| 张振宇等: ""1,10-邻二氮菲―铁(Ⅱ)―苦味酸盐三元配合物萃取-分光光度法测定痕量铁"", 《冶金分析》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106082324B (en) | 2018-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105899691B (en) | Scandium recovery method | |
| US9399804B2 (en) | Method for recovering scandium | |
| CN105293588B (en) | Preparation method for battery grade ferrous sulfate heptahydrate crystal | |
| CN106191463B (en) | A kind of purification method of zinc hydrometallurgy leachate | |
| CN104498714B (en) | Ferrum, aluminum, calcium, the method for titana matter is removed from containing scandium solution separates | |
| CN104388683B (en) | Method for separating and recycling vanadium and chromium from vanadium and chromium-containing material | |
| He et al. | Thermodynamic study on phosphorus removal from tungstate solution via magnesium salt precipitation method | |
| CN105506290B (en) | A kind of method of iron aluminum slag comprehensive utilization | |
| Chauhan et al. | A review on solvent extraction of nickel | |
| US4446115A (en) | Method of recovering tantalum from silicon-containing tantalum scrap | |
| CN103833156B (en) | A kind for the treatment of process of cold rolling chlorohydric acid pickling spent acid | |
| CN109609783A (en) | A method of efficiently separating purification palladium and rhodium from the alloy sheet containing palladium, rhodium alloy | |
| CN108603247A (en) | The recovery method of scandium | |
| CN106367606B (en) | A method of separating and recovering chromium from vanadium chromium waste residue | |
| JPH02503575A (en) | Separation and recovery of nickel and cobalt in ammoniacal systems | |
| CN100554453C (en) | A kind of leaching method of materials after nickelous oxide mine chloridization oxidation treatment | |
| CN107099672A (en) | The recovery method of the fume from steel making containing zinc | |
| CN106756091A (en) | A kind of extracting method of Metals of Discarded Printed Circuit Boards copper | |
| CN104862503B (en) | The method that scandium is extracted from lateritic nickel ore | |
| CN106082324B (en) | A kind of iron-free Zr (SO4)2Production method | |
| WO2016209178A1 (en) | Recovering scandium and derivatives thereof from a leach solution loaded with metals obtained as a result of leaching lateritic ores comprising nickel, cobalt and scandium, and secondary sources comprising scandium | |
| CN107601571A (en) | A kind of preparation method of ferric vandate | |
| JP2012206867A (en) | Method for producing molybdenum trioxide | |
| CN105236446B (en) | A kind of recycling method of waste hydrochloric acid | |
| CN110438339B (en) | Method for removing manganese in nickel hydroxide cobalt dissolving solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |