CN1788096A - A method of extracting copper from leach solutions at elevated temperatures - Google Patents
A method of extracting copper from leach solutions at elevated temperatures Download PDFInfo
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- CN1788096A CN1788096A CN 200480013190 CN200480013190A CN1788096A CN 1788096 A CN1788096 A CN 1788096A CN 200480013190 CN200480013190 CN 200480013190 CN 200480013190 A CN200480013190 A CN 200480013190A CN 1788096 A CN1788096 A CN 1788096A
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- extraction agent
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- salicylaldoxime
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Abstract
The invention relates to a method for extracting copper from an aqueous copper-bearing leach solution, wherein the temperature of the leach solution is at least 30 ℃. Such a method comprises: contacting the aqueous solution with an extractant of formula wherein R is a straight or branched chain C10－18Alkyl radical, R1Is H or CH3. These extractants do not undergo any significant degradation in the leach solution at temperatures greater than or equal to 30 c as occurs with conventional reagents.
Description
Related application intersects to be quoted from
It is the rights and interests of co pending provisional application sequence number 60/470657 on the 15th May in 2003 that the application has required the applying date, and these contents are hereby incorporated by.
Background technology
At present, extracting copper adopts the way of pressure leaching process or the booster action leaching in steel basin by iron ion or bacterium usually from copper concentrate or high-grade copper sulfide ore, and this just causes infusion solution to have high relatively temperature.Now, the temperature of most of infusion solution to be processed is greatly about 15 ℃-25 ℃.The temperature of infusion solution depends on leaching technology in pressure leaching container or steel basin, can be up to 150 ℃.Because a variety of causes, comprise the stability of the extraction agent of copper solvent, at high temperature handle infusion solution and have a lot of difficulties by the copper solvent extraction method.Therefore these infusion solutions will be cooled to before entering copper solvent extraction plant and be no more than about 45-50 ℃.
In the copper solvent extraction plant (SX) of commercial employing elevated temperature leaching technology, extraction molecule 5-nonyl salicyl aldooxime quilt is with 2,2, and 4-front three-1 mixes mutually in 3-pentanediol two isobutyrates and uses, and the commerce of this salt is called TXIB.TXIB belongs to an a kind of compounds that is called equilibrium modifier, and it is disclosed in United States Patent (USP) 4507268 and 6231784, is incorporated herein by reference at this full content with these two patents.Properties-correcting agent can change a normal copper extracting power of extraction agent, therefore make people need conscientiously select 5-nonyl salicyl aldooxime and for specific copper solvent extraction is used for optimum or near the mixing solutions of optimum properties-correcting agent.
What the operator of copper solvent extraction plant was concerned about is the hydrolytic deterioration of extraction agent such as 5-nonyl salicyl aldooxime etc., because the degraded of extraction agent can bring the problem of fringe cost and operation.Fringe cost occurring is because the loss of the extraction agent that causes owing to degrading must be compensated caused.
Operational issue occurs and be because extraction agent, will be higher than the degradation rate of properties-correcting agent, like this for some time ratio of 5-nonyl salicyl aldooxime and properties-correcting agent will be slowly in the SX extraction plant afterwards decline as the degradation rate of 5-nonyl salicyl aldooxime.Along with the mixture of this ratio decline 5-nonyl salicyl aldooxime and properties-correcting agent concerning with certain specific copper solvent extraction plant, no longer being optimum value.Optimum value for 5-nonyl salicyl aldooxime in the holding device and TXIB mixed solution, these two kinds of compounds all must adopt complicated analytical equipment to monitor, and for the appropriate mixing of 5-nonyl salicyl aldooxime in the assurance device and properties-correcting agent, the operator must calculate the amount of the pure 5-nonyl salicyl aldooxime that must add according to the conventional benchmark of normal copper solvent extraction agent.
This is explanation just, needs a kind of copper extraction molecule more stable than 5-nonyl salicyl aldooxime, reducing the number of times that extraction agent is degraded and runs off and reduce complex analyses, and these analyses be for the suitable ratio that keeps copper extraction molecule and properties-correcting agent necessary.
Summary of the invention
The invention belongs to a kind of from aqueous copper solution the method for extracting copper, wherein the temperature of aqueous copper solution is minimum is 30 ℃.This method comprises: aqueous copper solution is contacted with a kind of extraction agent with structural formula (I), and R is the C of a straight chain or side chain here
10-18Alkyl, R
1Be H or CH
3In temperature was greater than or equal to 30 ℃ infusion solution, the degradation rate of extraction agent of the present invention in degradation process was significantly less than the normal degradation rate that adopts traditional extraction agent.
Embodiment
Extraction agent of the present invention is a kind of compound with structural formula (I):
Wherein R is the C of a straight chain or side chain
10-18Alkyl, R
1Be H or CH
3R in compound with structural formula (I)
1During for H, it can be according to U.S. Patent No. 4,020, and 105 or No.4,020,106 described method preparation, perhaps by to according to U.S. Patent No. 4,085, the oximate of 146 aldehydes that make obtains.The full content of this several patents all is introduced into this paper as a reference.Be the R in the compound of (I) when having structural formula
1Be CH
3The time, it can pass through English Patent GB1, and 322,532 methods of describing make.Preferred extraction agent comprises: 2-hydroxyl-5-decyl acetophenone oxime, 2-hydroxyl-5-dodecyl methyl phenyl ketone oxime, 2-hydroxyl-5-pentadecyl acetophenone oxime, 5-decyl salicylaldoxime, 5-dodecyl salicylaldoxime and 5-pentadecyl salicylaldoxime and composition thereof.
Extraction agent of the present invention can and generally can both be dissolved in a kind of commercial hydrocarbon solvent such as CONOSOL 170ES, ORFOM SX7, and ORFOM SX12, ORFOM SX11, in Shellsol 2046 and the similar solvent, the concentration of this solvent is greater than about 0.25M.Organic extractant also can comprise a kind of equilibrium modifier, and properties-correcting agent can comprise a kind of ester, as pure isooctane-1, and 3-glycol diisobutyrate, adipic acid-di-n butyl ester, a kind of ketone, a kind of ether or a kind of alcohol such as tridecyl alcohol.This organic extractant can comprise additional oxime extraction agent.The temperature range of aqueous feed solution can be more than or equal to 30 ℃, 35 ℃ or 40 ℃.The concentration of copper generally changes between 50gpl Cu at about 5gpl Cu in the aqueous feed solution, most preferably greater than 10gpl Cu.Leach liquor can obtain by pressure oxidation or the bio-oxidation processing to certain enriched material.
The following examples are used for explanation but are not limitations of the present invention.
Embodiment
In the time of 45 ℃, contain 30gpl (grams per liter) Cu and 180gpl vitriolic water and a kind of organic extractant mutually, carried out a series of stability test by continuously stirring.Approximately the organic phase of the water of 350ml and 350ml is placed into 1 liter of round bottom glass flask of 3-neck of a standard, and a stirring motor is equipped with at its top, Teflon blade stirrer and a Friedrigs condenser.For controlled temperature at 45 ℃, flask is placed in the constant temperature oil bath.Mixing speed is made as 480rpm.The organic extractant sample is periodically taken out and is analyzed the maximum extraction amount of copper and the content of oxime.
In test 1, organic phase is 0.0463M in 5-nonyl salicyl aldooxime, and organic phase is 0.0425M in 5-dodecyl salicylaldoxime, and organic phase is 0.104M in Di-n-butyl Adipate, is dissolved among the CONOSOL 170ES.It the results are summarized in table 1.
Table 1
| Time (my god) | 5-nonyl salicyl aldooxime (m/l) | 5-dodecyl salicylaldoxime (m/l) |
| 0 | 0.0463 | 0.0425 |
| 56 | 0.0333 | 0.0362 |
| 84 | 0.0273 | 0.0328 |
| 112 | 0.0220 | 0.0292 |
| 139 | 0.0189 | 0.0266 |
| 168 | 0.0174 | 0.0260 |
| 196 | 0.0146 | 0.0233 |
| 224 | 0.0109 | 0.0189 |
| 252 | 0.0084 | 0.0154 |
| 260 | 0.0081 | 0.0149 |
By test data as can be known, the 5-nonyl salicyl aldooxime transformation period approximately is 115 days, is significantly less than 5-dodecyl salicylaldoxime, and under this experiment condition, its transformation period approximately is 220 days.
In test 2, organic phase is 0.2640M in 2-hydroxyl-5-nonylacetophenone oxime (ketoxime), organic phase in 5-nonyl salicyl aldooxime (C9Aldox) is 0.3091M, organic phase in 5-dodecyl salicylaldoxime (C12 Aldox) is 0.0202M, is dissolved among the CONOSOL 170ES.Test result is summarized in table 2.
Table 2
| Time (my god) | Ketoxime (m/l) | C9 Aldox(m/l) | C12 Aldox(m/l) |
| 0 | 0.2640 | 0.3091 | 0.0202 |
| 28 | 0.2403 | 0.2253 | 0.0158 |
| 56 | 0.2243 | 0.1823 | 0.0134 |
| 84 | 0.2086 | 0.1522 | 0.0123 |
| 112 | 0.1947 | 0.1274 | 0.0113 |
| 140 | 0.1833 | 0.1130 | 0.0107 |
| 168 | 0.1709 | 0.1012 | 0.0098 |
| 196 | 0.1611 | 0.0928 | 0.0089 |
| 224 | 0.1529 | 0.0868 | 0.0081 |
| 252 | 0.1475 | 0.0829 | 0.0078 |
By test data as can be known, the 5-nonyl salicyl aldooxime transformation period approximately is 83 days, and the transformation period of 5-dodecyl salicylaldoxime is 170 days, significantly greater than 5-nonyl salicyl aldooxime.2-hydroxyl-5-nonylacetophenone oxime is significantly stable than these two kinds of aldoximes, and its transformation period was above 330 days under this experiment condition.
Claims (19)
1, a kind of comprising by aqueous copper solution is contacted with a kind of extraction agent with structural formula (I), to be at least the method for extracting copper this aqueous copper solution of 30 ℃ from temperature, R is the C of straight chain or side chain in the formula
10-18Alkyl, R
1Be H or CH
3
2, the method for claim 1 is characterized in that extraction agent further is made up of hydrocarbon diluent.
3, the method for claim 1 is characterized in that R is the C of straight chain or side chain in the formula
10-18Alkyl, and R
1Be H.
4, the method for claim 1 is characterized in that R is the C of straight chain or side chain in the formula
10-18Alkyl, and R
1Be CH
3
5, the method for claim 1 is characterized in that extraction agent is selected from: 2-hydroxyl-5-decyl acetophenone oxime, 2-hydroxyl-5-dodecyl methyl phenyl ketone oxime, 2-hydroxyl-5-pentadecyl acetophenone oxime, 5-decyl salicylaldoxime, 5-dodecyl salicylaldoxime and 5-pentadecyl salicylaldoxime.
6, method as claimed in claim 5 is characterized in that extraction agent is a 5-dodecyl salicylaldoxime.
7, method as claimed in claim 5 is characterized in that extraction agent is 2-hydroxyl-5-dodecyl methyl phenyl ketone oxime.
8, method as claimed in claim 5 is characterized in that extraction agent is a 5-decyl salicylaldoxime.
9, method as claimed in claim 5 is characterized in that extraction agent is 2-hydroxyl-5-decyl acetophenone oxime.
10, method as claimed in claim 5 is characterized in that extraction agent is 2-hydroxyl-5-pentadecyl acetophenone oxime.
11, method as claimed in claim 5 is characterized in that extraction agent is a 5-pentadecyl salicylaldoxime.
12, the method for claim 1 is characterized in that extraction agent further is made up of the properties-correcting agent that is selected from ester, ketone, ether and alcohol.
13, method as claimed in claim 12 is characterized in that alcohol is three nonylcarbinols.
14, method as claimed in claim 12 is characterized in that ester is 2,2,4-trimethylammonium Skellysolve A-1,3-glycol diisobutyrate, hexanodioic acid dibutyl ester.
15, the method for claim 1 is characterized in that this temperature is 35 ℃.
16, a kind of comprising by aqueous copper solution is contacted with a kind of composition, to be at least the method for extracting copper 30 ℃ the aqueous copper solution from a kind of temperature, said composition comprises the extraction agent that (a) is made up of a kind of compound with structural formula (I), and wherein R is a dodecyl, and R
1Be H and (b) hexanodioic acid dibutyl ester
17, a kind of comprising by aqueous copper solution is contacted with a kind of composition, to be at least the method for extracting copper 30 ℃ the aqueous copper solution from a kind of temperature, said composition comprises the extraction agent that (a) is made up of a kind of compound with structural formula (I), and wherein R is a nonyl, and R
1Be CH
3(b) hexanodioic acid dibutyl ester
18, method as claimed in claim 16 is characterized in that temperature is 35 ℃.
19, method as claimed in claim 17 is characterized in that temperature is 35 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47065703P | 2003-05-15 | 2003-05-15 | |
| US60/470,657 | 2003-05-15 | ||
| US10/829,597 | 2004-04-22 |
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| Publication Number | Publication Date |
|---|---|
| CN1788096A true CN1788096A (en) | 2006-06-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480013190 Pending CN1788096A (en) | 2003-05-15 | 2004-04-27 | A method of extracting copper from leach solutions at elevated temperatures |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736158B (en) * | 2010-01-13 | 2012-12-19 | 郑州市德众化学试剂厂 | a copper extractant |
| CN104995319A (en) * | 2013-03-18 | 2015-10-21 | 国立大学法人九州大学 | Valuable-metal extraction method |
| CN108048653A (en) * | 2011-02-25 | 2018-05-18 | 考格尼斯知识产权管理有限责任公司 | Improved metal solvent extracts reagent and application thereof |
| CN109913648A (en) * | 2019-03-13 | 2019-06-21 | 广东省资源综合利用研究所 | Application and composite extractant and extraction system of the 2- hydroxyl arone oxime compound as extractant in extraction field |
| CN114561538A (en) * | 2022-03-03 | 2022-05-31 | 重庆康普化学工业股份有限公司 | Extracting agent of adjacent hydroxyl aromatic olefin ketoxime with conjugated double bonds |
-
2004
- 2004-04-27 CN CN 200480013190 patent/CN1788096A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736158B (en) * | 2010-01-13 | 2012-12-19 | 郑州市德众化学试剂厂 | a copper extractant |
| CN108048653A (en) * | 2011-02-25 | 2018-05-18 | 考格尼斯知识产权管理有限责任公司 | Improved metal solvent extracts reagent and application thereof |
| CN108048653B (en) * | 2011-02-25 | 2020-03-03 | 考格尼斯知识产权管理有限责任公司 | Improved metal solvent extraction reagents and uses thereof |
| CN104995319A (en) * | 2013-03-18 | 2015-10-21 | 国立大学法人九州大学 | Valuable-metal extraction method |
| CN104995319B (en) * | 2013-03-18 | 2016-10-19 | 国立大学法人九州大学 | Valuable metal extracting process |
| CN109913648A (en) * | 2019-03-13 | 2019-06-21 | 广东省资源综合利用研究所 | Application and composite extractant and extraction system of the 2- hydroxyl arone oxime compound as extractant in extraction field |
| CN114561538A (en) * | 2022-03-03 | 2022-05-31 | 重庆康普化学工业股份有限公司 | Extracting agent of adjacent hydroxyl aromatic olefin ketoxime with conjugated double bonds |
| CN114561538B (en) * | 2022-03-03 | 2024-02-06 | 重庆康普化学工业股份有限公司 | Hydroxy-like aryl ketene oxime extractant with conjugated double bond |
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