CN102212687A

CN102212687A - Application of 2-hydroxy-5-nonylacetophenone oxime (HNAO) in novel efficient extractant

Info

Publication number: CN102212687A
Application number: CN2011101352659A
Authority: CN
Inventors: 钱峰; 江亚俊
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-05-24
Filing date: 2011-05-24
Publication date: 2011-10-12

Abstract

The invention discloses an application of 2-hydroxy-5-nonylacetophenone oxime (HNAO) in a novel efficient extractant. In the invention, in order to better develop the extraction effect of the HNAO, the HNAO is compounded with N-902, the advantages and disadvantages of the two extractants are complementary, and the obtained compounded system has the strong extracting power and fast reaction ability of the oxime extractant as well as the easy back-extraction property and excellent physical properties of the ketoxime extractant, thus the compounded extractant can be most widely applied to the industry; and at present, only the foreign imported Lix984 series of products are available in the market but no related products are produced in China. The compounded product fills up a domestic gap and can replace the foreign imported Lix984 series of products, and the price of the compounded product is only two thirds of that of the foreign product; and the HNAO and N-902 compounded extractant can be taken not only as a copper extractant but also as a cobalt-nickel extractant.

Description

2-hydroxyl-the application of 5-nonylacetophenone oxime in new and effective extraction agent

Technical field

The present invention relates to the extraction agent of chemical field, relate in particular to a kind of extraction agent that from spent etching solution or low-grade copper mine, reclaims copper.

Background technology

Copper is one of most important strategy metal, is one of valuable source of national economy.Along with Chinese society doctrine fast development of market economy, China has become the big copper state that uses of the first in the world, also is first scarce copper state.Associated minerals are many altogether, grade is low (mostly below 1%) for China's copper mine, pass through the production of decades in addition, the a lot of copper mines of China have entered the exploitation later stage, and rich ore, easily closely exhaustion of ore dressing resource are so the L-SX-EW technology of the low-grade copper mine of suitable treatment has had very big development in China in recent years.The L-SX-EW technology successfully is used in the industry in China and handles low grade copper oxide ore and secondary copper sulfide mineral, and along with the progress of leaching-out technique, copper leaching rate also improves gradually.But carrying out along with exploitation, head grade constantly descends, the leach liquor copper content also descends thereupon, leach liquor impurities total amount also improves relatively, pH value variation range is more and more wider, but present copper extractant applicable pH value scope is all less, low to the copper solutions percentage extraction of the low high impurity of copper, therefore exploitation is applicable to that the wide highly selective copper extractant of material liquid pH value variation range becomes the research tendency of copper extractant.Except low-grade copper oxide ore and secondary copper sulfide mineral, China still has the low-grade chalcopyrite that is unsuitable for pyrometallurgical smelting in a large number.The extract technology of handling chalcopyrite both at home and abroad is ripe, but the leach liquor cupric and the chlorine dose of most of extract technologies are too high, the lifting capacity of existing copper extraction agent also is not enough to the load high-copper, so that extraction again behind the leach liquor need Macrodilution, and the copper extractant of therefore developing high loading necessitates.In addition, along with the manufacturing development of China, produced a large amount of contained waste liquids, waste material, only the Kunshan, Jiangsu just produces more than 300,000 ton of copper sludge every year, the discharging of contained waste liquid can produce serious environmental and pollute, could safety dumping after copper scrap goods such as simultaneously a large amount of waste printed circuit boards also need reclaim.In recent years, rising violently significantly of world market copper valency influenced the manufacturing development of China to a great extent, traced it to its cause, and copper resource organic efficiency lowly is one of reason.Adopt the L-SX-EW technology to be reclaimed copper, solve problem of environmental pollution simultaneously.This solution has become inexorable trend.Certainly, foreign technology is very unripe, otherwise just a large amount of useless line level, copper scrap goods etc. can not exported to China.Trace it to its cause, efficient, low-loss extraction agent is this key problem in technology place.At present, main still fat class organic compound and the mixture thereof that adopts in the coppersmith industry extraction agent, this compounds has the C=N-carbon-to-nitrogen double bon that can not rotate.Because hydrogen atom can be replaced by metal in the oxime, and nitrogen-atoms has unpaired electron, therefore can form certain huge legendary turtle cyclization structure, also must have another electron donor on the oxime molecule, perhaps having another can be by the hydrogen atom group of metal replacement, thereby form N-N or N-O coordination compound, thereby the realization huge legendary turtle is closed the extraction that realizes cupric ion.Its advantage of extraction that strong huge legendary turtle mould assembly fat is used for high copper content solution is: to a certain extent, because after adopting acid to strip in solution, there is and can be used for compensation in the cyclical operation in a large amount of copper with the huge legendary turtle compound, thereby can reduce the waste of copper.The minimizing of closing copper along with huge legendary turtle in the circulating system can significantly promote the extraction of whole process copper.Research is found simultaneously, if contain certain aldehydes matter in the reverse-extraction agent amount that reclaims copper from solvent phase is obviously increased.For acidic solution, generally the oximes extraction agent of Cai Yonging comprises ketoxime and salicylaldoxime, can be referred to as O-hydroxyaryl oxime, and the effect of extracting of its mixture is better than adopting the occasion of single extraction agent.For effective extraction of high copper-containing solution and metal back extraction fast be the alkyl salicylate aldoxime particularly amino group have a notable attribute of branched alkyl group (containing 5 carbon at least) and composition thereof.Employed light basic fat mainly comprises ketone fat and aldehyde fat two big classes at present.Industrial copper extractant commonly used mainly comprises: the Cyanex series product of the LIX of HenkelCorporation company (Liquid ion exehanger) series product, the Kelex of A Xilan chemical company series product and U.S. empire chemical company.Most typical representative is a LIX series, and such mixture has association's collection effect, has the good reextraction and the physicals of the extracting power of aldoxime and kinetics, ketoxime concurrently, is to use one of maximum copper extractants at present in the world.Hydroxyl oximes extraction agent is the efficient extraction agent of copper, exists long alkane chain and active group (as phenolic hydroxyl group, oximido) in its molecule simultaneously, therefore has interfacial activity, easily in organic phase.Aqueous phase interface absorption, and reduce interfacial tension.Lix984N is that volume ratio is Lix860N and the mixture of Lix84 in high flash point kerosene of 1:1, the effective constituent of Lix860N is 2-hydroxyl-5-nonyl salicyl aldooxime, the effective constituent of Lix84 is 2-hydroxyl-5-nonylacetophenone oxime (HNAO), it to the extraction of Cu have that saturated capacity is big, kinetics speed is fast, selectivity good, extraction efficiency is high, stable performance, the extraction of adaptation low ph condition and need not advantage such as additive, have broad application prospects.

At present, the internal copper extraction agent is various in style, and the extraction agent of existing large-scale production has 2-hydroxyl-5-nonyl salicyl aldooxime extraction agent (N-902) at home; the N-902 extraction agent is characterized in: extremely strong collection copper ability, and rate of extraction is fast, collection copper recovery height; but the back extraction difficulty, property is poor.

Summary of the invention

The object of the invention is to provide a kind of 2-hydroxyl-application of 5-nonylacetophenone oxime (HNAO) in new and effective extraction agent, characteristics according to 2-hydroxyl-5-nonylacetophenone oxime (HNAO) and 2-hydroxyl-5-nonyl salicyl aldooxime extraction agent (N-902), 2-hydroxyl-5-nonylacetophenone oxime (HNAO) with the 2-hydroxyl-5-nonyl salicyl aldooxime extraction agent (N-902) carries out composite, not only have extremely strong extracting power, and have back extraction very easily, consume less, characteristics that cost is low.

The technical scheme that realizes the object of the invention is:

A kind of 2-hydroxyl-application of 5-nonylacetophenone oxime (HNAO) in new and effective extraction agent, it is characterized in that: 2-hydroxyl-5-nonylacetophenone oxime (HNAO) and 2-hydroxyl-5-nonyl salicyl aldooxime extraction agent (N-902) is pressed the preparation of 1:1 mass ratio, with obtaining composite extraction agent after 40% the solvent oil dilution.

Described composite extraction agent is as the extraction agent of copper, cobalt and nickel.

The present invention compared with prior art has following advantage:

1.HNAO and N-902 is composite, the relative merits of two kinds of extraction agents can be complementary, compound system can have the easy back extraction and the good physical of the high extracting power of oxime extraction agent and quick reaction capability, ketoxime extractants concurrently, it is the maximum extraction agent of industrial application, at present, the Lix984 series product that have only external import on the market, domestic also do not have a relevant products production.This composite product has been filled up domestic blank, can subrogate country outside the Lix984 series product of import, price only is 2/3rds of an external product.2.HNAO not only can be used as copper extractant with the composite extraction agent of N-902, can also be as the extraction agent of cobalt and nickel.

Embodiment

Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention, and all technical schemes that are equal to also belong to category of the present invention, and scope of patent protection of the present invention should be limited by every claim.

A kind of 2-hydroxyl-application of 5-nonylacetophenone oxime (HNAO) in new and effective extraction agent, 2-hydroxyl-5-nonylacetophenone oxime (HNAO) and 2-hydroxyl-5-nonyl salicyl aldooxime extraction agent (N-902) is pressed the preparation of 1:1 mass ratio, with obtaining composite extraction agent after 40% the solvent oil dilution.

Claims

1. the 2-hydroxyl-application of 5-nonylacetophenone oxime in new and effective extraction agent, it is characterized in that: 2-hydroxyl-5-nonylacetophenone oxime (HNAO) and 2-hydroxyl-5-nonyl salicyl aldooxime extraction agent (N-902) is pressed the preparation of 1:1 mass ratio, with obtaining composite extraction agent after 40% the solvent oil dilution.

2. a kind of 2-hydroxyl according to claim 1-application of 5-nonylacetophenone oxime in new and effective extraction agent, it is characterized in that: described composite extraction agent is as the extraction agent of copper, cobalt and nickel.