CN85100736B - To remove iron from sulfate sulutions by extraction - Google Patents
To remove iron from sulfate sulutions by extractionInfo
- Publication number
- CN85100736B CN85100736B CN85100736A CN85100736A CN85100736B CN 85100736 B CN85100736 B CN 85100736B CN 85100736 A CN85100736 A CN 85100736A CN 85100736 A CN85100736 A CN 85100736A CN 85100736 B CN85100736 B CN 85100736B
- Authority
- CN
- China
- Prior art keywords
- iron
- extraction
- back extraction
- primary amine
- grams per
- 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.)
- Expired
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention belongs to the fields of wet metallurgy and inorganic salt preparation, namely that a new extraction system is provided. A synergistic extraction system is composed of bai-an, long chain alcohol or neutral phosphorus (phosphine), and inert solvent. Selective extraction and iron removal are carried out in a weak acidic water solution, iron can be effectively and back extracted with dilute sulphuric acid, and the problem of difficult back extraction is solved. Compared with the prior art, the dosage of back extraction agents is reduced by ten times, and a pathway is provided for industrial application.
Description
The invention belongs to hydrometallurgy and inorganic salt preparation field, promptly study a kind of new extraction system, from the sulphuric leachate of ore, concentrate etc., remove impurity iron (Fe effectively
+ 3), the iron in the load organic phase can be used the dilute sulphuric acid back extraction.
In the field such as hydrometallurgy and inorganic chemicals industry, the normal raw materials such as sulfuric acid decomposing ore, concentrate that adopt, iron is as impurity, together enter solution with valuable metal, as directly leaching zinc sulfide concentrates from conventional wet zinc metallurgy process and high pressure, sulfuric acid decomposes pyrolusite, sulfuric acid to leach contains in the immersion liquid such as cobalt nickel materials, exploring cost-effective method for removing iron, to improving the quality of products, reducing production costs, all is vital.And for example Tai-Ace S 150 is basic kinds of inorganic salt, and it has extensive use at aspects such as papermaking, paint, printing and dyeing, water purification, and the quality of Tai-Ace S 150 depends on iron-holder in the product.As make iron level (Fe in fine papers and the special paper requirement Tai-Ace S 150
2O
3Meter)≤0.02%, deironing from alum liquor is an important topic in the inorganic chemicals industry.
Method for removing iron is broadly divided into four classes: (1) makes iron with Fe
2O
3NH
2The O form is removed from solution; (2) separate out with the form precipitation of dry oxidation iron; (3) remove from solution with double salt or complex salt form; (4) with ion-exchange or solvent extration, from solution, remove.First three methods all produces solid slag, has the solid-liquid separation problem, operates more loaded down with trivial detailsly, and labour intensity is big, and metal recovery rate is not high, and solid slag is because of reasons such as foreign matter contents, and still difficult the application caused and stacked and secondary pollution problems.
Along with the development of solvent extraction technology, the theory and the technical study of carrying out with the extraction process deironing come into one's own.Successively explored with deironing from alum liquor such as secondary amine, acid phosphatase fat from 1967-1979 as U.S. mineral bureau; The Soviet Union, Japan report D2EHPA(di-(2-ethylhexyl)phosphoric acid), carboxylic acid, carboxylate salt extraction process and ion exchange method deironing from alum liquor; China Zibo Acid Making Plant, Shandong Prov. cooperates to carry out the low carbon fatty acid extraction with Kweiyang magnalium studying and designing institute and removes iron tests, but de-ferrous effect is undesirable; Schultze L.E etc. are with JMT deironing from Tai-Ace S 150 (see the U.S. mineral bureau report US.Bur.MinesRI8353).Academy of sciences's Shanghai organic chemistry is studied with primary amine (N-1923 or 7101) deironing from alum liquor, and the 5th institute of Ministry of Nuclear Industry is also studied with primary amine deironing and finished expanding test from Tai-Ace S 150.The comprehensive literature report is easier to realize with extraction process deironing ratio, but how with the back extraction effectively of iron in the organic phase, does not find reasonable approach as yet.Primary amine collection iron effect is fine, but must use effectively back extraction iron of the 6-8N vitriol oil, is can be not rational economically, and is also inconvenient in the operation.
The present invention seeks to study a kind of new extraction system, it not only has good collection ferrum property, the prior just back extraction iron effectively of dilute sulphuric acid that is to use solves " back extraction difficulty " problem, so that provide effective way for extraction process industrial application of deironing from sulfuric acid medium.
The present invention uses primary amine and long-chain alcohol or neutral phosphonic (phosphine) class to give the synergistic extractant system of body reagent and inertia solution composition, from the pH value is selectivity collection iron the sulfuric acid medium of 1-2, used primary amine is the dialkyl methyl amines of secondary carbon(atom) type, or the trialkyl methylamine of tertiary carbon atom type, structural formula is write a Chinese character in simplified form and is respectively R
1R
2CHNH
2, R
1R
2R
3CNH
2, R wherein
1R
2R
3The carbonatoms of base can be identical, also can be different.Can add other groups on the carbochain, total carbon atom is 12-25, and producing 1-nonyl-decyl amine as pilot plant of homemade N-1923(Shanghai Organic Chemistry Institute, Chinese Academy of Sciences is main primary amine mixture), to produce 1-octyl group-nonyl amine be main primary amine mixture in 7101(Beijing the 5th institute), the U.S. produces JMT etc.Used long-chain alcohol (C
7-C
15) comprise secondary carbon alcohols, n-Octanol, decyl alcohol.Experiment finds that secondary carbon(atom) alcohol is better than the straight chain alcohols, considers from economic angle, uses the secondary octanol of industrial reagent more reasonable; Used neutral phosphonic (phosphine) class comprises TBP, P
350(methyl-phosphorous acid diformazan heptyl ester), TRPO, TOPO add these neutral body reagent of giving, and can improve the percentage extraction of iron, and significantly reduce reverse-extraction agent sulfuric acid consumption.Table 1 is listed the effect of primary amine-neutral phosphonic (phosphine) class deironing from Tai-Ace S 150.
The Phosphorus deironing from Tai-Ace S 150 of table 1. primary amine-neutrality
(aqueous phase liquid Fe(III) 2.21 grams per liters, A 135 grams per liters, pH1.57O/A=1,5 minutes, 13-14 ℃.Organic phase is the 5%7101-octane)
| Organic phase is formed | Balance organic phase Fe grams per liter | E% | ||
| 7101% | The neutral phosphonic title | Neutral phosphonic % | ||
| 5 | O | 1.305 | 59.1 | |
| 5 | TBP | 2.5 | 1.59 | 72.0 |
| 5 | 7.5 | 1.87 | 84.7 | |
| 5 | 15 | 1.96 | 88.7 | |
| 5 | 30 | 1.98 | 89.6 | |
| 0 | 30 | ～0 | ～0 | |
| 5 | P 350 | 2.5 | 1.46 | 66 |
| 5 | 7.5 | 1.72 | 77.8 | |
| 5 | 15 | 1.87 | 84.7 | |
| 5 | 30 | 1.98 | 89.6 | |
| 5 | TRPO | 2.5 | 1.98 | 89.4 |
| 5 | 7.5 | 2.04 | 92.5 | |
| 5 | 15 | 2.02 | 91.5 | |
| 5 | 26 | 1.87 | 84.4 | |
| 5 | TRPO | 2 | 1.78 | 80.6 |
| 5 | 4 | 1.95 | 88.2 | |
| 5 | 10 | 2.01 | 91.0 | |
| 0 | 10 | ～0 | ～0 | |
Extraction conditions of the present invention is: initial material liquid pH 1-2 is for well; Primary amine and neutral phosphonic (phosphine) class or long-chain alcohol consumption are looked the selected optimum value of iron-holder and the deironing degree of depth in the feed liquid, and the primary amine consumption can be in the 2.5-20% scope, neutral phosphonic (phosphine) class consumption in the 15-40% scope or the long-chain alcohol consumption in the 40-70% scope; Temperature raises, and percentage extraction slightly descends, and operates getting final product starting time 2-3 minute in 14-40 ℃.
Compare and the feed liquid iron-holder, initial acidity and extractant concentration are relevant, and when pH was 1-2, can be in organic loading iron ratio: the ratio of amine (mol)/iron (grammeatom)=3-4/1 be selected.Iron aluminium separation factor β Fe/Al＞10
4In actually operating, multi-stage counter current extraction and reextraction can be adopted, also cross current solvent extraction can be adopted.
But characteristics of the present invention are to use just back extraction iron of dilute sulphuric acid.Table 2 is listed pure primary amine-kerosene organic phase and the comparison that adds back extraction result behind the synergist, shows when not adding secondary octanol, can not back extraction iron with dilute sulphuric acid, and promptly use 3N sulfuric acid also can only obtain 62.8% single-stage back extraction ratio.
Add secondary octanol and not only can significantly improve the extracting power of iron, and can significantly improve the back extraction ratio of iron.Curve 1 is iron content 2.51 grams per liters in the feed liquid among the figure, aluminium 54 grams per liters, extraction is 5%N-1923 with organic phase, be in a ratio of organic phase/water=1/1, starting time 3 minutes, the experimental result that room temperature is 28 ℃, curve 2 for negative iron organic phase back extraction curve condition for adding the ratio NH of the grammeatom number of load iron in sulfuric acid equivalents and the organic phase
+/ M(Fe)=10, starting time 3 minutes is in a ratio of organic phase/water=2.As seen from the figure, when adding the acid amount equally, the iron in simple primary amine-kerosene organic phase is not by back extraction; When the alcohol amount was higher in the organic phase, though the percentage extraction of iron descends, the back extraction ratio of iron significantly increased.Liquid pH＜0.9 after the back extraction.
Back extraction temperature applicable range broad, not high 14-15 ℃ of following organic phase viscosity yet, can be 14-40 ℃ of range operation.
Effect of extracting of the present invention is identical with prior art, and the back extraction effect sees Table 3, and reverse-extraction agent amount ratio prior art reduces more than ten times.
It is effective equally that extraction system of the present invention is used for other sulfate system deironing.The neutrality of zinc hydrometallurgy leaching slag adopts the leaching of high temperature sulfuric acid, obtains containing the leaching liquid of a large amount of iron, and iron-holder is generally the 12-15 grams per liter, adopts yellow phosphate ferrovanadium process to remove 80% iron, keeps 1-3 grams per liter iron, so that deeply removing arsenic, antimony.As adopt the present invention can replace the jarosite operation; Make process simplification, labour intensity reduces.From containing zinc 80 grams per liters, single-stage collection iron in the iron content 10 grams per liter sulphuric acid solns can make in the solution iron level less than 3 grams per liters with primary amine-secondary octanol (or TBP)-kerosene organic phase.
Use the secondary octanol-kerosene of 7.5%N-1923-40%, compare 1/1 ,～15 ℃ of extractions, contain manganese 110 grams per liters, iron 5.59 grams per liter sulphuric acid solns, twice iron extraction 95% of cross-flow,
Example one, four-stage counter-current continuous extraction test
Equipment: mixer-settlers, 100 milliliters of mixing section volumes, aqueous phase liquid are bauxite sulfuric acid to leach liquid, contain the Fe1.08 grams per liter, the Al32 grams per liter, the Si0.100 grams per liter reaches a small amount of Ca, Mg, Na, K, Mn etc., pH1.55, organic phase consists of the secondary octanol-kerosene of 7.5%N-1923-60%, about 4 minutes of the single-stage residence time of extraction, room temperature 14-15 ℃, throughput ratio O/A=1/1.Fe＜0.050 grams per liter in the alum liquor behind the level Four extraction iron, pH3.0-3.10, β Fe/Al＞1.6 * 10
4
Example two, six stage countercurrent extraction test
Organic phase composition and extraction conditions are with example one.
Aqueous phase liquid contains the Fe2.43 grams per liter, the Al41 grams per liter, and the Si=0.10 grams per liter reaches small amount of impurities Ca, Mg, Na, K etc., pH1.64, after the extraction of six stage countercurrents, Fe in the alum liquor＜0.040 grams per liter, pH2.8-2.9, aluminium amount in the organic phase＜0.050 grams per liter, β Fe/Al＞4 * 10
4
Extract iron in example three, the zinc sulfide concentrates high-pressure leaching liquid
Aqueous phase liquid Fe9.908-11 grams per liter, Zn80 grams per liter and a small amount of Cd, Mg, As, Sb etc., pH1.15, O/A=1/1,15 ℃, starting time 5 minutes.
15%N-1923-kerosene iron percentage extraction 50%;
The secondary octanol of 15%N-1923-40%-kerosene iron percentage extraction 73.3%;
15%N-1923-15%TBP-kerosene iron percentage extraction 74.3%;
15%N-1923-40%TBP-kerosene iron percentage extraction 72.1%;
Secondary octanol-the kerosene of 7.5%N-1923-20%, iron-holder in the solution＜0.50 grams per liter behind twice cross current solvent extraction, zinc＜0.010 grams per liter in the load organic phase.
Example four, multi-stage countercurrent back extraction iron tests
Organic phase is formed the secondary octanol-kerosene of 7.5%N-1923-60%, load iron 2.04 grams per liters, aluminium 0.023 grams per liter, back extraction progression: six grades, the 3-4 minute single-stage residence time, the sulfuric acid consumption is 0.30N by comparing O/A=1/1, back extraction is flowed than O/A=2/1-3/1,14-15 ℃ of back extraction temperature, iron content in the poor organic phase＜0.050 grams per liter after the back extraction, liquid pH0.70-0.80 after the iron content back extraction, iron content 4.5-5.5 grams per liter.
Claims (5)
1, from sulfate solution, extracts the method for deironing with the 2.5-50% primary amine, it is characterized in that adding the long-chain alcohol (C of 40-70%
7-C
15) or neutral phosphonic (phosphine) class of 15-40% and the synergistic extractant system that inert solvent is formed, under solutions of weak acidity, extract iron, with dilute sulphuric acid (as 0.5-1N) back extraction iron.
2,, it is characterized in that used primary amine comprises that N-1923(1-nonyl-decyl amine is main primary amine mixture by the described method of claim 1), 7101(1-octyl group-nonyl amine is main primary amine mixture), neutral phosphonic is TBP, long-chain alcohol is secondary octanol.
3,, it is characterized in that extracting under the acidic conditions that initial pH is 1-2 and carry out by claim 1,2 described methods.
4,, it is characterized in that liquid pH＜0.90 after the back extraction by claim 1,2 described methods.
5,, it is characterized in that extraction and back extraction temperature are at 14-40 ℃ by claim 1,2 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100736A CN85100736B (en) | 1985-04-01 | 1985-04-01 | To remove iron from sulfate sulutions by extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100736A CN85100736B (en) | 1985-04-01 | 1985-04-01 | To remove iron from sulfate sulutions by extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100736A CN85100736A (en) | 1986-07-30 |
| CN85100736B true CN85100736B (en) | 1987-11-11 |
Family
ID=4791399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85100736A Expired CN85100736B (en) | 1985-04-01 | 1985-04-01 | To remove iron from sulfate sulutions by extraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85100736B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6962685B2 (en) * | 2002-04-17 | 2005-11-08 | International Business Machines Corporation | Synthesis of magnetite nanoparticles and the process of forming Fe-based nanomaterials |
| CN105314665B (en) * | 2014-07-16 | 2017-10-31 | 华东理工大学 | One kind compounding ferric sulfate extractant |
-
1985
- 1985-04-01 CN CN85100736A patent/CN85100736B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85100736A (en) | 1986-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102453801B (en) | Method for separating zirconium and hafnium | |
| DE2702779A1 (en) | PROCESS FOR MAKING ZINC FROM A MATERIAL CONTAINING ZINC AND IRON | |
| US3907966A (en) | Nickel extraction and stripping using oximes and ammoniacal carbonate solutions | |
| AU621163B2 (en) | Method for separating interfering elements from valuable metal electrolyte solutions | |
| CN107557598B (en) | The method for preparing V electrolyte | |
| CN110002509A (en) | A kind of ferric trichloride crystal and its preparation method and application | |
| CN109852797A (en) | A method of extractant and its extraction and separation elemental lithium for extraction and separation elemental lithium | |
| CN106521190A (en) | Purpose and method of amido-contained neutral phosphine extracting agent for extracting and separating zirconium and/or hafnium | |
| US3966872A (en) | Coupled cationic and anionic method of separating uranium | |
| CN107828961A (en) | A kind of extracting process of rare earth element ion and obtained rare-earth enrichment liquid | |
| DE3725611A1 (en) | METHOD FOR THE JOINT SEPARATION OF STONE ELEMENTS FROM VALUE METAL ELECTROLYTE SOLUTIONS | |
| US3966873A (en) | Uranium complex recycling method of purifying uranium liquors | |
| US3923976A (en) | Process for recovery of zinc from solutions that contain it as a result of extraction with solvents for their adaptation to electrolysis | |
| US4624704A (en) | Selective recovery of zinc from metal containing brines | |
| CN113979476A (en) | Method for preparing ammonium tetramolybdate product by back extraction and impurity removal | |
| CN85100736B (en) | To remove iron from sulfate sulutions by extraction | |
| CN114672650B (en) | Method for extracting scandium from titanium white waste acid by using bisphosphonic acid extractant | |
| CN107674974B (en) | The purposes and method of the phosphine extractant extraction and recovery copper of neutrality containing amino | |
| Reddy et al. | Separation and recovery of cobalt and nickel from sulfate solutions of Indian Ocean nodules using Cyanex 272 | |
| US4383978A (en) | Process of obtaining uranium and uranium compounds from phosphoric acid | |
| CN86100720B (en) | Extraction of iron from aluminium sulfate solution with tertiary amine | |
| CN112481489B (en) | Synergistic extraction agent and method for selectively extracting cobalt from acidic cobalt-containing solution by using same | |
| CN1005409B (en) | Phase transfer back extraction in iron extraction with acidic phosphate (phosphonate) | |
| US4256716A (en) | Process for treating loaded extractant from purification of phosphoric acid by extraction | |
| US2780519A (en) | Recovery of uranium from ores |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| PB01 | Publication | ||
| C06 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |