CN1070229A - A kind of emulsion liquid membrane is carried gold and is reclaimed sodium cyanide technology - Google Patents
A kind of emulsion liquid membrane is carried gold and is reclaimed sodium cyanide technology Download PDFInfo
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- CN1070229A CN1070229A CN91106223A CN91106223A CN1070229A CN 1070229 A CN1070229 A CN 1070229A CN 91106223 A CN91106223 A CN 91106223A CN 91106223 A CN91106223 A CN 91106223A CN 1070229 A CN1070229 A CN 1070229A
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- emulsion
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A kind of emulsion liquid membrane is carried gold and is reclaimed the sodium cyanide processing method, be to extract by cyaniding, system breast, liquid film, the several master operations of breakdown of emulsion and electrorefining are formed, it is characterized in that making in the newborn operation in the phase solution water-soluble reverse-extraction agent be to adopt alkali, basic salt or in alkali, add certain salt.This technological operation is simple, facility investment is few, gold recovery high (can reach 98%).And prussiate can carry out recycling use, can avoid the pollution of prussiate to environment effectively.The oil phase of this technology extraction simultaneously can cyclically utilizing, and process cost is low, is easy to apply industrial.
Description
The invention provides a kind of method of utilizing emulsion liquid membrane from rare alkaline gold sodium cyanide solution, to extract concentrated gold and reclaiming sodium cyanide.
In recent years, along with gold production constantly develops, seek to develop new resource and more and more paid attention to by people with recycling low-grade gold.The heap leaching method that adopts in the mining industry is exactly one of effective ways of handling low grade ore.This technology has advantages such as method is simple, recovery of the capital is fast, and production time is short.But gold content concentration is extremely low in the heap leaching solution, and only 1～2PPm adopts traditional interpolation zinc replacement, and carbon slurry method or carbon soak the investment of method required equipment can't be realized greatly.As adopting direct electrolysis method, gold concentration is too low in your liquid, electrical efficiency is low, power consumption is high, expense is expensive owing to leach, therefore also difficult enforcement.Being fit to one of this method that reclaims precious metal from dilute solution is the liquid film technology that grew up in recent years, it is a kind of new isolation technique of carrying out on the technical foundation of traditional liquid-liquid extraction, it has broken inherent equilibrium-limited in the conventional solvent abstraction technique, the extraction in the solvent extraction and two processes of stripping is merged into a step finish.After containing the appearance of carrier liquid film, it is similar to microbial film, makes solute against the concentration gradient transmission, demonstrates the function of height enrichment method.Close with the technology used in the present invention, in the membrane science technical journal (1989,9(4), 39) once reported and utilize emulsion liquid membrane to extract gold.This process flow diagram as shown in Figure 1.Its process is: will pulverize Gold Ore and make cyaniding leach liquor 2 through cyaniding 1, will make breast 3 again and make milk sap, and be distributed to and carry out liquid film extraction 4 processing in the leach liquor 2.Then liquid after extracting 4 processing through liquid film is separated, its raffinate can turn back to the cyaniding operation and recycle as heap leaching solution, and isolated milk sap is carried out breakdown of emulsion 5.High density through separating again behind the breakdown of emulsion 5 after obtaining enrichment contains golden liquid, but directly carries out electrolysis 6 preparing high-purity gold, and the newborn 3 raw materials circulation of the emulsion liquid membrane organic phase system of can be used as system breast is used.
In above-mentioned technology, system breast 3 is that the preparation of milk sap is an important procedure, and it is to contain flowing carrier, and the organic solvent of tensio-active agent is made milk sap with interior fully the mixing of containing water-soluble reverse-extraction agent under certain speed.Known cyanating solution with gold is that process object adopts in the emulsion liquid membrane gold extraction technology, and reverse-extraction agent often utilizes thiocarbamide and hydrochloric acid.But the gold of thiocarbamide after as the reverse-extraction agent enrichment is difficult to smelt and obtains proof gold, and thiocarbamide not only costs an arm and a leg, and it still is a kind of carcinogenic substance.In above-mentioned acid system, can generate simultaneously hypertoxic hydrocyanic acid, so this kind technology is difficult in the industry and uses.
The objective of the invention is to overcome the shortcoming of above-mentioned processing method, provide a kind of improved emulsion liquid membrane to put forward golden novel process, this technology is suitable for directly extracting gold and can reclaim sodium cyanide from rare alkaline sodium cyanide solution (gold mine vat liquor).Utilize the rate of recovery height, simple to operate of this technology gold, and can solve the environmental pollution of general cyanidation gold-extracted factory.The organic oil phase that uses in this technology can cyclically utilizing in addition, can further reduce productive expense and be suitable for suitability for industrialized production and use.
Emulsion liquid membrane of the present invention is carried gold and reclaimed sodium cyanide technology is to improve on the processes well known basis and a kind of novel process of proposing, and the schematic flow sheet shown in the still available accompanying drawing 1 of its technical process is represented.Promptly this technology comprises that cyaniding 1, cyaniding leach liquor 2, system breast 3, liquid film extraction 4, breakdown of emulsion 5 and electrorefining concentrate several master operations such as golden liquid system proof gold 6, it is characterized in that making adopting following method in newborn 3 operations:
1, prepares certain density tensio-active agent, mutually water-soluble back extraction reagent in the oil-phase solution of carrier and organic solvent composition reaches.Wherein surfactant content (accounting for the oil phase concentration of volume percent) is: 0.1～20%; Vector contg is 1～25%; Surplus is organic solvent.Its preferred concentration is a surfactant content 0.5～5%, vector contg 2～8%.Water-soluble concentration of anti-stripping agent in the interior phase solution (phase solution weight percent concentration in accounting for) is: 0.1～15%.Its preferred concentration is 0.5～5%.
2, be 0.1～20 mixed by volume with the oil-phase solution that is mixed with interior solution mutually,, for example carry out emulsification in colloidal mill, ultrasonic emulsator or the employing high speed agitator and make Water in Oil emulsion at emulsor.
In above-mentioned system breast 3 operations, in another key character of the present invention is in the phase solution water-soluble back extraction reagent be to adopt to add a certain amount of (be not more than alkali or basic salt amount 50%) salt, for example sodium hydroxide or potassium, calcium hydroxide, yellow soda ash or potassium, sodium pyrosulfate or potassium, sodium sulfate or potassium, sodium-chlor etc. in alkali, basic salt or alkali or the basic salt.Organic solvent in the oil-phase solution can be a non-polar solvent in addition, for example alkanes hexane, heptane, octane, decane, dodecane, n-Hexadecane etc.; Aromatic hydrocarbons is as benzene, dimethylbenzene etc. or other petroleum products such as kerosene, solar oil, machine oil, heavy gas oil, Valelinum Liquidum, petroleum naphtha etc.Tensio-active agent can adopt poly-two succimide, poly-only son's diamide, C
4The sulfonated bodies of olefin copolymer, one or more mixtures in the sulfonated bodies of polyhutadiene, anhydrous sorbitol oleic acid monoester or anhydrous sorbitol oleic acid three esters.Carrier can adopt the commercial goods acidic extractant, chelating extractant, and neutral phosphonic oxygen extraction agent, the organic amine extraction agent is or/and big cyclammonium kind of extractants.Wherein acidic extractant can adopt n-nonanoic acid, the dibutyl phosphate of phenylformic acid, acid phosphoric acid ester etc.; Chelating extractant such as oxine, 2-methyl-oxine etc.; Neutral phosphonic oxygen extraction agent can adopt dibutyl butylphosphonate, dibutyl phosphonic acids butyl ester, tributylphosphine oxide, tributyl phosphate, methyl-phosphorous acid diformazan heptyl ester, phosphodiester, 2-ethylhexyl phosphoric acid monoesters, trioctylphosphine oxygen phosphorus; Amine extractant can adopt two-(1-isobutyl--3,5-dimethyl hexyl) amine, positive trioctylamine and macromole amine.
In the method provided by the present invention, its liquid film extracts 4 operations can be undertaken by batch operation or continous way operation.Batch operation is distributed to the milk sap of making in the cyaniding leach liquor that fills alloy, stirs the milk sap uniform particles is scattered in the feed liquid timing sampling analysis at a slow speed.The continous way operation is generally carried out in column extractor, and the cyaniding leach liquor enters from the column extractor upper end, and extracting phase (residual phase) flows out through heavy clear section.Milk sap enters from the lower end of pillar, and by dispersed with stirring in feed liquid, flow out in cohesion back, pillar top then.Through liquid film extract 4 handle after isolating milk sap enter emulsion treater and carry out breakdown of emulsion 5 operations.Residual phase (water) sodium cyanide-containing behind the breakdown of emulsion can be used as and proposes golden mother liquor (ore immersion liquid) circulation recovery use.At present, generally believe that the liquid film breaking method is to adopt the high-voltage electrostatic demulsifying method preferably, the present invention has adopted high pressure static electricity spark emulsion treater can finish breakdown of emulsion 5 operations smoothly at normal temperatures.Main component tensio-active agent and the carrier to liquid film is harmless behind the breakdown of emulsion simultaneously, the water ratio that reclaims oil phase is not high, not adding under the film phase component, can recycle repeatedly, extraction yield and enrichment factor do not have obvious influence, below by example content of the present invention are described further.
Example 1, intermittent type emulsion liquid membrane are carried gold and are reclaimed the sodium cyanide test
The preparation water-in-oil emulsion, oil-phase solution (volume ratio) is an anhydrous sorbitol oleic acid monoester 5%, tri-n-octyl amine 4%, polyhutadiene 2%, kerosene 89% is with 1% weight Na
2CO
3The aqueous solution slowly was added in the oil phase ratio 1: 1, used strong row to stir, and about 15 minutes of 3000 rev/mins of stirring velocitys are made a kind of water in oil milk sap of stablizing.Slowly being scattered in Gold Content after milk sap prepares is in the stock liquid of the 2PPm left and right sides, after after a while, Au(CN has taken place promptly)
- 2, CN
-Migration, the milk sap after the extraction is put into the emulsion treater breakdown of emulsion, the concentration of water gold is listed in the table 1 with the atomic absorption spectrophotometry test-results.
Table 1 milk sap collection gold and cyanide ion result
Test raw material liquid (PPm) raffinate (relief liquor) is concentrated solution (PPm) percentage extraction (PPm)
Au
+CN
-Au
+CN
-Au
+CN
-Au
+% CN
-%
1 2.5 150 0.09 0.5 98 4586 96.4 99.7
2 1.9 170 0.10 0.47 70 5120 94.7 99.7
Example 2 continuous emulsifying liquid membrane extraction of gold and the test of recovery sodium cyanide
The composition of water-in-oil emulsion and preparation method are identical with example 1 identical/stock liquid, and the made milk sap of getting ready is pumped in the container for storing liquid, are entered on material liquid tank is delivered to column extractor by pump containing golden stock liquid then.Column extractor in this experiment is made by synthetic glass, diameter 90mm, one meter of virtual height, be divided into 6 cells, there is a stirring rake every chamber, stirring arm is driven by direct-current machine, available voltate regulator is regulated rotating speed, raffinate (relief liquor) flows out through heavy clear section, and milk sap is delivered to ingress, column extractor lower end by pump from the emulsion tank pump and entered column extractor, is dispersed into fine particle by stirring rake and moves up and the feed liquid countercurrent flow, emulsion behind the collection gold is after the cohesion of pillar top, flow out by emulsion exit, pillar upper end, enter emulsion treater and carry out breakdown of emulsion, breakdown of emulsion 10 minutes, can obtain the high density alloy solution, the newborn device of the oil phase system of entering continues to use.Analytical procedure is identical with example 1.Test-results is listed in the table 2.
Table 2 continuous countercurrent collection gold and cyanide ion data
Extraction time (branch) raffinate (PPm) concentrated solution (PPm)
Au
+CN
-Au
+CN
-
0 1.58 20.5
1 0.049 1.11 71.23 1043.75
2 0.054 1.84 96.58 1082.26
3 0.099 2.09 88.47 1163.59
4 0.079 1.87 105.20 1163.59
5 0.104 3.11 105.85 1163.59
Example 3, oil phase is reused test
Press example 1 described processing condition, reclaim oil phase and make 1 test of newborn operation repetition example again behind breakdown of emulsion, its test-results is listed in table 3.
Table 3 oil phase is reused test
Experiment number raw material (PPm) raffinate (PPm) percentage extraction %
Au
+CN
-Au
+CN
-Au
+CN
-
1 3.34 180.91 0.72 8.19 78.55 95.47
5 2.82 195.83 0.55 9.59 80.70 95.11
10 3.02 177.78 0.45 9.17 85.00 94.84
15 2.70 168.50 0.61 5.65 81.00 96.64
20 2.75 197.30 0.53 7.60 80.90 96.10
25 2.50 181.70 0.37 6.40 85.00 96.50
30 2.40 171.70 0.39 7.50 83.30 96.50
The raffinate of above-mentioned experiment can be incorporated in the ore steeping fluid and recycles.Gold content is lower than 0.05PPm in the last relief liquor, and gold recovery can reach more than 98%.Discharge simultaneously that the cyanogen root is lower than 0.5PPm from concentration in the tail washings.Above-mentioned experiment is carried out 30 extraction oils and is recycled repeatedly mutually, is not adding under the film phase component, and percentage extraction does not have obvious influence.
By above-mentioned example, adopt method provided by the invention, its technological operation is simple, and facility investment is few, gold recovery is high, and prussiate can carry out recycling use, can avoid the pollution of prussiate to environment effectively.Simultaneously, owing to adopt high pressure static electricity spark device breakdown of emulsion, do not damage the film phase composite, the oil phase of extraction can cyclically utilizing, so process cost is low, is easy to apply industrial.
Claims (4)
1, a kind of utilize emulsion liquid membrane to carry gold and reclaim the sodium cyanide processing method comprise several master operations such as cyaniding, system breast, liquid film extraction, breakdown of emulsion and electrorefining, in it is characterized in that making in the newborn operation in the phase solution water-soluble back extraction reagent be to adopt to add a certain amount of salt in alkali, basic salt or alkali or the basic salt, for example sodium hydroxide or potassium, calcium hydroxide, yellow soda ash or potassium, sodium pyrosulfate or potassium, sodium-chlor etc., the salts contg that is added are not more than 50% of alkali or basic salt amount.
2, carry gold and reclaim the sodium cyanide processing method according to claim 1 is described, it is characterized in that the concentration of volume percent of making oil-phase solution in the newborn operation is: tensio-active agent: 0.1～20%; Carrier: 1～25%, surplus is organic solvent; Phase solution weight percent was 0.1～15% in water-soluble concentration of anti-stripping agent accounted in the interior phase solution.
3, carry gold and reclaim the sodium cyanide processing method according to claim 2 is described, the concentration of volume percent that it is characterized in that making oil-phase solution preferable in the newborn operation is a surfactant content: 0.5～5%, and vector contg: 2～8%, surplus is organic solvent; Phase solution weight percent was 0.5～5% in water-soluble concentration of anti-stripping agent accounted in the interior phase solution.
4, carry gold and reclaim the sodium cyanide processing method according to claim 1 is described, it is characterized in that described breakdown of emulsion operation utilizes high pressure static electricity spark emulsion treater, carry out at normal temperatures.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91106223A CN1029792C (en) | 1991-08-30 | 1991-08-30 | Process for extracting gold and recovering sodium cyanide by emulsifying liquid film method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91106223A CN1029792C (en) | 1991-08-30 | 1991-08-30 | Process for extracting gold and recovering sodium cyanide by emulsifying liquid film method |
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| Publication Number | Publication Date |
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| CN1070229A true CN1070229A (en) | 1993-03-24 |
| CN1029792C CN1029792C (en) | 1995-09-20 |
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| CN91106223A Expired - Fee Related CN1029792C (en) | 1991-08-30 | 1991-08-30 | Process for extracting gold and recovering sodium cyanide by emulsifying liquid film method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303007C (en) * | 2004-03-29 | 2007-03-07 | 同济大学 | Method for fabricating micropowder of lead chromate through coupling treatment of waste water of lead and chrome |
| CN1317054C (en) * | 2004-11-11 | 2007-05-23 | 武汉理工大学 | Liquid membrane emulsion and its usage |
| CN101962718A (en) * | 2010-09-16 | 2011-02-02 | 长春黄金研究院 | Liquid film for extracting gold from alkaline solution |
| CN104831068A (en) * | 2015-05-05 | 2015-08-12 | 大连理工大学 | Emulsion membrane for separating calcium and magnesium ions |
| CN114262795A (en) * | 2021-12-27 | 2022-04-01 | 南开大学 | Water-in-oil emulsion and preparation method and application thereof |
| US11319613B2 (en) | 2020-08-18 | 2022-05-03 | Enviro Metals, LLC | Metal refinement |
-
1991
- 1991-08-30 CN CN91106223A patent/CN1029792C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303007C (en) * | 2004-03-29 | 2007-03-07 | 同济大学 | Method for fabricating micropowder of lead chromate through coupling treatment of waste water of lead and chrome |
| CN1317054C (en) * | 2004-11-11 | 2007-05-23 | 武汉理工大学 | Liquid membrane emulsion and its usage |
| CN101962718A (en) * | 2010-09-16 | 2011-02-02 | 长春黄金研究院 | Liquid film for extracting gold from alkaline solution |
| CN104831068A (en) * | 2015-05-05 | 2015-08-12 | 大连理工大学 | Emulsion membrane for separating calcium and magnesium ions |
| US11319613B2 (en) | 2020-08-18 | 2022-05-03 | Enviro Metals, LLC | Metal refinement |
| US11578386B2 (en) | 2020-08-18 | 2023-02-14 | Enviro Metals, LLC | Metal refinement |
| CN114262795A (en) * | 2021-12-27 | 2022-04-01 | 南开大学 | Water-in-oil emulsion and preparation method and application thereof |
| CN114262795B (en) * | 2021-12-27 | 2023-03-14 | 南开大学 | Water-in-oil type emulsion and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1029792C (en) | 1995-09-20 |
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