CN103741174B - Separate the method containing tin liquor ferrous ions - Google Patents
Separate the method containing tin liquor ferrous ions Download PDFInfo
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- CN103741174B CN103741174B CN201310730096.2A CN201310730096A CN103741174B CN 103741174 B CN103741174 B CN 103741174B CN 201310730096 A CN201310730096 A CN 201310730096A CN 103741174 B CN103741174 B CN 103741174B
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- tin liquor
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Abstract
A kind of method separated containing tin liquor ferrous ions of disclosure, contacts with containing tin liquor including by extractant, and is separated with containing tin liquor by extractant, and it is characterized in that, the molecular formula of described extractant is R3N, wherein, R is the alkyl of C8-C10; Described containing hydrogen cloride concentration >=140g/L in tin liquor. The employing present invention can by ferrous ion from containing extract and separate direct tin liquor out, and extraction yield is up to more than 98.7%, and keeps the extraction yield that stannous ion is low, and even as low as less than 0.65%, and extractant is reusable, lower in cost.
Description
Technical field
The invention belongs to the separation of ferrous ion, be specifically related to the separation containing tin liquor ferrous ions.
Background technology
In electroplating industry, the application of electrotinning is widely. Acidic Sn electroplating layer has that variable color anticorrosive, resistance to, soldering nontoxic, easy, softness, fusing point be low and the advantage such as ductility is good, also has good decorative effect. Therefore tin coating can as solderable coating, it is possible to use as decorative coating. By special pre-treating technology, the surface of composite formed be firmly combined with, alloy layer fine and close, bright, uniform. In certain scope, it might even be possible to replace silvering, reduce the murder by poisoning degree to human body, be widely used in the industries such as electrician, electronics, food, light industry.
When carrying out tin plating technique, it is necessary to the operation of a step bright tin plating layer. Because tin plating electrolyte is highly acid, inevitably steel strip substrate being produced corrosiveness, thus there will be ferrous ion in the plating solution, and accumulating in the plating solution so that the corrosion resistance of coating, soldering and soft heat glossiness etc. are substantially reduced; Meanwhile, the Sn (II) in tin plating electrolyte will be become Sn (IV) by the dioxygen oxidation in air, and the existence of the ferrous ion more catalysis speed of this kinds of oxidation reaction, cause serious muddiness, be substantially reduced the performance of plating solution.
Solvent extraction is a kind of effectively isolation technics of maturation, is widely used in the industry such as hydrometallurgy, plating. Compared with the sedimentation method, the advantage of extraction and separation technology is mainly that technological process is short, industrial chemicals and energy resource consumption is relatively low, metal recovery rate is high etc.
In reported extraction deferrization process, it is usually and first Fe (II) is oxidized to Fe (III), extract and separate ferrum again, but, when Fe (II) and Sn (II) coexists, during oxidizing Fe (II), Sn (II) also will be aoxidized, deferrization process is caused to complicate, in addition can because extracting the partial loss causing stannum while stannum.
N235Belong to basic extractant, be the mixing Trifatty amine based on C8��C10, molecular formula: R3N, wherein R is the alkyl of C8-10, and industrial goods are colourless or light yellow clear oily liquids, N at normal temperatures235Extracting each metal ion species ability is from big to small: Zn2+��Fe3+��Cu2+��Co2+��Fe2+��Ni2+Deng, namely the N of Fe (III)235Complex is more than the N of Fe (II)235Complex is more stable, therefore uses N at present235The research of extract and separate ferrum is mainly in the separation of ferrum (III), and for being directly separating Fe (II), especially in tin plating electrolyte or the extract and separate research of high concentration stannous ion acid solution ferrous ions also seldom.
Summary of the invention
It is an object of the invention to provide a kind of from the method going out ferrous ion containing extract and separate tin liquor.
It is as follows that the present invention realizes the technical scheme that above-mentioned purpose adopts:
A kind of method separated containing tin liquor ferrous ions, contacts with containing tin liquor including by extractant, and is separated with containing tin liquor by extractant, it is characterised in that the molecular formula of described extractant is R3N, wherein, R is the alkyl of C8-C10; Described containing hydrogen cloride concentration >=140g/L in tin liquor.
Further, described containing hydrogen cloride concentration >=180g/L in tin liquor.
Further, described is 180��250g/L containing hydrogen cloride concentration in tin liquor.
Further, described extractant organic solvent diluting.
Further, described organic solvent is kerosene or petroleum ether.
Further, extractant with when contacting containing tin liquor, temperature >=50 DEG C.
Further, extractant is with when contacting containing tin liquor, and temperature is 50��60 DEG C.
Further, described is sub-solution of tin containing tin liquor.
Further, by extractant with separate containing tin liquor after in the extract that obtains back extraction go out the process of ferrous ion: include contacting hydrochloric acid with extract, and isolate aqueous phase again.
Further, described concentration of hydrochloric acid is 0.05��1.5mol/L.
Further, described concentration of hydrochloric acid is 0.5��1mol/L.
During back extraction, preferred 1:(2��10 of volume ratio of extract and hydrochloric acid). It is preferably 1:(3��5).
Trifatty amine is for the ferrous ion in the solution of tin of extract and separate Asia, and the molecular formula of described Trifatty amine is R3N, wherein, R is the alkyl of C8-C10.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further details.
If no special instructions, described in an embodiment of the present invention liquid to be extracted and N235Extractant obtains each through following method:
By (NH4)2Fe(SO4)2��6H2O is dissolved in the aqueous hydrochloric acid solution of 20mL2mol/L, then constant volume is to 100mL, is configured to the ferrous standard solution of 0.1mol/L; By SnCl2��6H2O is dissolved in the aqueous hydrochloric acid solution of 20mL2mol/L, then constant volume is to 100mL, is configured to the sub-stannum standard solution of 0.1mol/L. Realize concentration to demarcate before use and determine.
The sub-stannum standard solution of the ferrous standard solution of above-mentioned 20mL and 20mL is mixed, is configured to the sub-solution of tin (hereinafter referred to as liquid to be extracted) containing ferrous ion.
Trioctylphosphine tertiary amine selected by extractant, and No. CAS: 1116-76-3, with the petroleum ether of 80mL, the trioctylphosphine tertiary amine of 20mL is diluted to the N that concentration is 20%235Extractant solution is (hereinafter referred to as N235Extractant).
Embodiment 1
In beaker, add liquid to be extracted and the 10mL400g/LHCl solution of 40mL, after mixing, add 5mLN235Extractant, by film seal, constant temperature water bath magnetic agitation, rotating speed is 20r/s, and extraction temperature is 50 DEG C, after stirring 20min, proceeds to and stands 15min layering in separatory funnel, collects water layer and organic layer respectively, and water layer is raffinate phase, and organic layer is extraction phase.
Embodiment 2
In beaker, add liquid to be extracted and the 20mL400g/LHCl solution of 40mL, after mixing, add 5mLN235Extractant, by film seal, constant temperature water bath magnetic agitation, rotating speed is 20r/s, and extraction temperature is 50 DEG C, after stirring 20min, proceeds to and stands 15min layering in separatory funnel, collects water layer and organic layer respectively, and water layer is raffinate phase, and organic layer is extraction phase.
Embodiment 3
In beaker, add liquid to be extracted and the 30mL400g/LHCl solution of 40mL, after mixing, add 5mLN235Extractant, by film seal, constant temperature water bath magnetic agitation, rotating speed is 20r/s, and extraction temperature is 50 DEG C, after stirring 20min, proceeds to and stands 15min layering in separatory funnel, collects water layer and organic layer respectively, and water layer is raffinate phase, and organic layer is extraction phase.
Embodiment 4
In beaker, add liquid to be extracted and the 40mL400g/LHCl solution of 40mL, after mixing, add 5mLN235Extractant, by film seal, constant temperature water bath magnetic agitation, rotating speed is 20r/s, and extraction temperature is 50 DEG C, after stirring 20min, proceeds to and stands 15min layering in separatory funnel, collects water layer and organic layer respectively, and water layer is raffinate phase, and organic layer is extraction phase.
Embodiment 5
In beaker, add liquid to be extracted and the 50mL400g/LHCl solution of 40mL, after mixing, add 5mLN235Extractant, by film seal, constant temperature water bath magnetic agitation, rotating speed is 20r/s, and extraction temperature is 50 DEG C, after stirring 20min, proceeds to and stands 15min layering in separatory funnel, collects water layer and organic layer respectively, and water layer is raffinate phase, and organic layer is extraction phase.
Embodiment 1��5(numbering respectively 1��5) extract and separate result see following table:
��
(adopting the Fe(II in spectrophotography and EDTA titration measuring sample) and Sn(II) concentration)
By above-mentioned experiment, can be seen that, the extraction yield of ferrous ion is directly by the impact of hydrogen cloride concentration in sub-tin liquor, as HCl concentration >=140g/L, Fe(II) extraction yield is up to 98.7%, but Sn(II) extraction yield also have 24%, as HCl concentration >=180g/L, Fe(II) extraction yield is up to 99.8%, and Sn(II) extraction yield low to less than 0.65%.
Under the same conditions, extract the time used extraction yield to ferrous ion and stannous ion and fluctuate within �� 0.5%, substantially without impact, generally can be controlled in 10��50min.
Under the same conditions, temperature during extraction to the fluctuation of extraction yield also within �� 0.5%, have substantially no effect on the extraction yield of ferrous ion and stannous ion, but temperature is lower than 50 DEG C, particularly when 20��40 DEG C, third phase organic facies easily occurs, namely extraction phase is divided into biphase, for avoiding the appearance of third phase, temperature can be arranged on more than 50 DEG C, preferably 50��60 DEG C, so can avoid adding adjuvant.
N235Extractant also can extract by a small amount of principle addition repeatedly.
Embodiment 6
Embodiment 5 being separated the extraction phase obtained mix with the HCl solution of 15mL0.05mol/L, fully shake back extraction, back extraction 1 time in pear shape separatory funnel, Stripping times is 3min. Back extraction stands 20min after terminating, and after clear layering, collects water layer strip liquor.
Embodiment 7
Embodiment 5 being separated the extraction phase obtained mix with the HCl solution of 15mL0.1mol/L, fully shake back extraction, back extraction 1 time in pear shape separatory funnel, Stripping times is 3min. Back extraction stands 20min after terminating, and after clear layering, collects water layer strip liquor.
Embodiment 8
Embodiment 5 being separated the extraction phase obtained mix with the HCl solution of 15mL0.5mol/L, fully shake back extraction, back extraction 1 time in pear shape separatory funnel, Stripping times is 3min. Back extraction stands 20min after terminating, and after clear layering, collects water layer strip liquor.
Embodiment 9
Embodiment 5 being separated the extraction phase obtained mix with the HCl solution of 15mL1.0mol/L, fully shake back extraction, back extraction 1 time in pear shape separatory funnel, Stripping times is 3min. Back extraction stands 20min after terminating, and after clear layering, collects water layer strip liquor.
Embodiment 10
Embodiment 5 being separated the extraction phase obtained mix with the HCl solution of 15mL1.5mol/L, fully shake back extraction, back extraction 1 time in pear shape separatory funnel, Stripping times is 3min.Back extraction stands 20min after terminating, and after clear layering, collects water layer strip liquor.
Embodiment 11
Embodiment 5 being separated the extraction phase obtained mix with the HCl solution of 15mL2.0mol/L, fully shake back extraction, back extraction 1 time in pear shape separatory funnel, Stripping times is 3min. Back extraction stands 20min after terminating, and after clear layering, collects water layer strip liquor.
Embodiment 6��11(numbering respectively 1��6) back extraction result see following table:
��
By back extraction result it can be seen that HCl solution concentration is more than after 1.0mol/L, ferrous ion stripping rate sharply declines, particularly at more than 1.5mol/L, as, during for 2.0mol/L, being little to back extraction and go out ferrous ion. Therefore, during back extraction, the concentration of HCl solution is preferably 0.05��1.5mol/L, and that more excellent is 0.5��1mol/L.
The N reclaimed after back extraction235Extractant is reused for the extraction of embodiment 5 ferrous ions, after repeating 5 times, Fe(II) extraction yield still up to 98.9%, and Sn(II) extraction yield low to less than 1.7%, there is good repeatability.
Claims (8)
1. separate the method containing tin liquor ferrous ions, contact with containing tin liquor including by extractant, and again extractant is separated with containing tin liquor, it is characterised in that the molecular formula of described extractant is R3N, wherein, R is the alkyl of C8-C10; Described containing hydrogen cloride concentration 140��250g/L in tin liquor.
2. separate the method containing tin liquor ferrous ions according to claim 1, it is characterised in that described is 180��250g/L containing hydrogen cloride concentration in tin liquor.
3. separate the method containing tin liquor ferrous ions according to claim 1, it is characterised in that described extractant organic solvent diluting.
4. separate the method containing tin liquor ferrous ions according to claim 3, it is characterised in that described organic solvent is kerosene or petroleum ether.
5. according to the Claims 1 to 4 arbitrary described separation method containing tin liquor ferrous ions, it is characterised in that extractant with when contacting containing tin liquor, temperature >=50 DEG C.
6. separate the method containing tin liquor ferrous ions according to claim 5, it is characterised in that extractant is with when contacting containing tin liquor, and temperature is 50��60 DEG C.
7. according to the Claims 1 to 4 arbitrary described separation method containing tin liquor ferrous ions, it is characterized in that, by extractant with separate containing tin liquor after in the extract that obtains back extraction go out the process of ferrous ion: include contacting hydrochloric acid with extract, and isolate aqueous phase again.
8. separate the method containing tin liquor ferrous ions according to claim 7, it is characterised in that described concentration of hydrochloric acid is 0.05��1.5mol/L.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100720A (en) * | 1986-02-05 | 1987-08-26 | 中国科学院化工冶金研究所 | With extracting deironing in the aluminium sulfate solution with tertiary amine |
| EP0675077A2 (en) * | 1994-03-30 | 1995-10-04 | Elkem A/S | Method for recovering metal chlorides from silicon or ferrosilicon alloys which have been reacted with chlorinating agents |
| CN103031437A (en) * | 2011-09-29 | 2013-04-10 | 深圳市格林美高新技术股份有限公司 | Processing method for waste liquid from stripping tin scolding |
| CN103215447A (en) * | 2013-04-16 | 2013-07-24 | 内蒙古科技大学 | Method for extracting scandium from scandium-enriched ferrous acid solution by using P204 |
-
2013
- 2013-12-26 CN CN201310730096.2A patent/CN103741174B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100720A (en) * | 1986-02-05 | 1987-08-26 | 中国科学院化工冶金研究所 | With extracting deironing in the aluminium sulfate solution with tertiary amine |
| EP0675077A2 (en) * | 1994-03-30 | 1995-10-04 | Elkem A/S | Method for recovering metal chlorides from silicon or ferrosilicon alloys which have been reacted with chlorinating agents |
| CN103031437A (en) * | 2011-09-29 | 2013-04-10 | 深圳市格林美高新技术股份有限公司 | Processing method for waste liquid from stripping tin scolding |
| CN103215447A (en) * | 2013-04-16 | 2013-07-24 | 内蒙古科技大学 | Method for extracting scandium from scandium-enriched ferrous acid solution by using P204 |
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