阅读说明：本技术 一种黄铜矿生物浸出的方法 (A kind of method of chalcopyrite Bioleaching ) 是由 贾炎 阮仁满 谭巧义 孙和云 于 2018-05-25 设计创作，主要内容包括：本发明提供了一种黄铜矿生物浸出的方法,所述方法为：向黄铜矿生物浸出体系中加入药剂,所述药剂包括表面活性剂和/或异噻唑啉酮类杀菌剂。本发明所述方法操作简便,成本较低,通过在生物浸出体系中添加药剂,控制微生物对亚铁的氧化过程,从而调节浸出溶液的电位,可有效解决黄铜矿浸出过程中因表面钝化而阻碍黄铜矿进一步浸出的问题,提高了黄铜矿的生物浸出率。(The present invention provides a kind of method of chalcopyrite Bioleaching, the methods are as follows: medicament is added into chalcopyrite Bioleaching system, the medicament includes surfactant and/or isothiazolinone biocide agent.The method of the invention is easy to operate, cost is relatively low, by adding medicament in Bioleaching system, microorganism is controlled to ferrous oxidation process, to adjust the current potential of infusion solution, it can effectively solve the problems, such as to hinder chalcopyrite further to leach because of surface passivation in chalcopyrite at lixiviating course, improve the Bioleaching rate of chalcopyrite.)

1. a kind of method of chalcopyrite Bioleaching, which is characterized in that the method are as follows: add into chalcopyrite Bioleaching system Enter medicament, the medicament includes surfactant and/or isothiazolinone biocide agent.

2. the method according to claim 1, wherein the surfactant includes quaternary ammonium salt, polyquaternium, alkane Any one in base benzene sulfonate, alkyl sulfate or alkylsulfonate or at least two combination.

3. method according to claim 1 or 2, which is characterized in that the isothiazolinone biocide agent includes 1,2- benzene And isothiazoline -3- ketone, 2-n- octyl -4- isothiazoline -3- ketone, 2-methyl-4-isothiazolin-3-one or 5- chloro-2-methyl - Any one in 4- isothiazole beautiful jade -3- ketone or at least two combination.

4. method according to claim 1-3, which is characterized in that the Bioleaching system includes microorganism heap Leaching system and/or microorganism leaching system；

Preferably, the Bioleaching system includes chalcopyrite ore, extracting solution and microorganism；

Preferably, the current potential of the Bioleaching system is maintained 580~700mV；

Preferably, when the current potential of the Bioleaching system is more than 700mV, medicament is supplemented into Bioleaching system.

5. according to the method described in claim 4, it is characterized in that, in the microorganism dump leaching system chalcopyrite ore partial size For P₈₀> 5mm, preferably 5~50mm；

Preferably, the partial size of chalcopyrite ore is P in the microorganism leaching system₈₀≤ 5mm, preferably 0.02~1mm.

6. method according to claim 4 or 5, which is characterized in that the extracting solution is that sulfuric acid and ferric mixing are molten Liquid；

Preferably, sulfuric acid concentration is 0.1~20g/L, preferably 5~15g/L in the extracting solution；

Preferably, ferric iron concentration is 0.1~50g/L, preferably 5~20g/L in the extracting solution.

7. according to the described in any item methods of claim 4-6, which is characterized in that the microorganism includes acidophilic microorganism；

Preferably, the acidophilic microorganism includes that Leptospirillum, Thiobacillus, irony Pseudomonas, Sulfobacillus or acid are micro- Any one in Pseudomonas or at least two combination；

Preferably, the acidophilic microorganism includes any one in iron-oxidizing bacteria, sulfur oxidizing bacterium or iron sulfur oxidizing bacterium or at least two The combination of kind；

Preferably, it acidophilic microorganism inoculation or is grown in the ore of Bioleaching system naturally or Bioleaching system In extracting solution；

Preferably, the acidophilic microorganism comes from any one in ore, tailing, extracting solution or acidic mine water or at least two Combination.

8. method according to claim 1-7, which is characterized in that the Adding Way of the medicament include directly with Ore in Bioleaching system is mixed and/or is dissolved in the extracting solution of Bioleaching system；

Preferably, when the medicament is directly mixed with the ore in Bioleaching system, the usage amount of the medicament is 5~ 1000mg/kg ore, preferably 10~100mg/kg ore；

Preferably, when the medicament dissolution is in the extracting solution of Bioleaching system, the usage amount of the medicament is 20~ 5000mg/L extracting solution, preferably 50~500mg/L extracting solution.

9. method according to claim 1-8, which is characterized in that extracting solution in the Bioleaching system into Row extraction, obtained raffinate are recycled as extracting solution.

10. -9 described in any item methods according to claim 1, which is characterized in that the method are as follows: to chalcopyrite Bioleaching Medicament is added in system, so that the current potential of the Bioleaching system is maintained 580~700mV, when the Bioleaching system Current potential when being more than 700mV, supplement medicament into Bioleaching system；

The Bioleaching system includes chalcopyrite ore, extracting solution and acidophilic microorganism, yellow when using microorganism dump leaching system The partial size of Copper ore is P₈₀> 5mm, when using microorganism leaching system, the partial size of chalcopyrite ore is P₈₀≤ 5mm, The extracting solution be sulfuric acid and ferric mixed solution, the sulfuric acid concentration be 0.1~20g/L, ferric iron concentration be 0.1~ 50g/L, acidophilic microorganism inoculation or is grown in the ore of Bioleaching system or the extraction of Bioleaching system naturally In liquid；

The medicament includes surfactant and/or isothiazolinone biocide agent, and the Adding Way of the medicament includes direct In the extracting solution for mixing and/or being dissolved in Bioleaching system with the ore in Bioleaching system, when the medicament directly with When ore in Bioleaching system mixes, the usage amount of medicament is 5~1000mg/kg ore, when the medicament dissolution is in life When in the extracting solution of object Leaching Systems, the usage amount of medicament is 20~5000mg/L extracting solution.

Technical field

The invention belongs to biological metallurgy technical fields, are related to a kind of method of chalcopyrite Bioleaching.

Background technique

Due to the development of human society, worldwide, high-grade copper ore resources are largely consumed, and copper resource tends to be poor Change, grade constantly reduces, and processing difficulty is gradually increased；Traditional flotation-pyrometallurgical smelting can not cost-effectively utilize the portion Divide Lean Copper Ores, and microorganism biological metallurgy becomes low-grade copper sulfide ores resource high-efficiency, warp with its unique advantage The important front edge technology of Ji exploitation.

Copper metal resource mainly exists with copper-sulphide ores, and chalcopyrite is the most important existence form of copper-sulphide ores. Chalcopyrite is a kind of primary sulfide ore of indissoluble, lattice energy with higher, thus is had on Chemical Leaching and Bioleaching The Bioleaching industrialization of certain difficulty, chalcopyrite fails to carry out on a large scale always.In chalcopyrite at lixiviating course, due to There are a large amount of iron ions in Leaching Systems, inevitably generate a large amount of ihleite, such precipitating compactness is very good, can be close Mineral surfaces are wrapped in, contact of the microorganism with mineral surfaces is prevented, influences leaching efficiency.Research finds that chalcopyrite biology soaks Passivation and high redox potential or height [Fe out³⁺]/[Fe²⁺] ratio is related, and the oxidation of ferrous oxidation microorganism, Improve [Fe³⁺]/[Fe²⁺] ratio, the current potential of infusion solution also correspondinglys increase, and ihleite precipitating more easily generated is unfavorable for biology The progress of leaching process.

Currently, strengthen chalcopyrite Bioleaching main method have high temperature leach, reduce pH value, addition surfactant, Metal cation and low potential system etc., for attempting the problem of passivation of solution chalcopyrite.103993171 A of CN is disclosed A method of addition nonionic surfactant promotes chalcopyrite Bioleaching, by room temperature Acidithiobacillus ferrooxidans strain GF Nonionic surfactant is added during Chalcopyrite Leaching, changes mineral surface hydrophobicity and permeability, and it is raw to solve chalcopyrite The problem that leaching velocity is slow in object leaching process, leaching rate is low, but this method still has limitation, can not change the oxygen of ferrous ion Change process, the current potential of control system, while nonionic surfactant be not significant to the effect of passivation layer, the life to chalcopyrite It is limited that object leaches castering action.

In conclusion strengthen the Bioleaching of chalcopyrite, it need to also be from the oxidation for inhibiting ferrous ion, regulation Leaching Systems electricity Position aspect is improved.

Summary of the invention

In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of method of chalcopyrite Bioleaching, The method in Bioleaching system by adding medicament, the process of regulating and controlling microbial ferrous oxide, to control solution Current potential reduces the formation of passivating film, promotes the Bioleaching of chalcopyrite.

To achieve this purpose, the present invention adopts the following technical scheme:

The present invention provides a kind of method of chalcopyrite Bioleaching, the methods are as follows: to chalcopyrite Bioleaching system Middle addition medicament, the medicament include surfactant and/or isothiazolinone biocide agent.

In the present invention, in chalcopyrite Bioleaching, due to the oxidation of ferrous ion, propose the oxidation-reduction potential of solution Height promotes the passivation of chalcopyrite, and by the way that surfactant or isothiazolinone biocide agent is added, then it can inhibit this Process, this is because surfactant can destroy protein and cause microorganism generation by the integrality of influence microbial cell It thanks to exception, inhibits the activity of microorganism to a certain extent, it is dead to even result in part microorganism；Isothiazolinone biocide agent The quantity of microorganism can be significantly reduced, to reduce the activity of its ferrous oxide.Iron of the addition of the above medicament to microorganism Oxidation activity is affected, and relatively small on the oxidation of sulphur influence, to promote the Bioleaching of chalcopyrite.

It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.

As currently preferred technical solution, the surfactant includes quaternary ammonium salt, polyquaternium, alkyl benzene sulphonate Any one in salt, alkyl sulfate or alkylsulfonate or at least two combination, the combination is typical but non-limiting reality Example has: the combination of the combination of quaternary ammonium salt and polyquaternium, quaternary ammonium salt and alkyl sulfate, alkylbenzene sulfonate and alkylsulfonate Combination, quaternary ammonium salt, alkyl sulfate and combination of alkylsulfonate etc..

As currently preferred technical solution, the isothiazolinone biocide agent includes 1,2- benzisothiazole- 3- ketone, 2-n- octyl -4- isothiazoline -3- ketone, 2-methyl-4-isothiazolin-3-one or 5- chloro-2-methyl -4- isothiazole beautiful jade - Any one in 3- ketone or at least two combination, the combination is typical but non-limiting example has: 1,2- benzisothiazole- The combination of 3- ketone and 2-n- octyl -4- isothiazoline -3- ketone, 2-methyl-4-isothiazolin-3-one and 5- chloro-2-methyl -4- are different The combination of thiazole beautiful jade -3- ketone, 1,2-benzisothiazolin-3-one, 2-n- octyl -4- isothiazoline -3- ketone and 2- methyl -4- are different The combination etc. of thiazoline -3- ketone.

As currently preferred technical solution, the Bioleaching system includes microorganism dump leaching system and/or micro- life Object leaching system.

Preferably, the Bioleaching system includes chalcopyrite ore, extracting solution and microorganism.

Preferably, the current potential of the Bioleaching system is maintained 580~700mV, for example, 580mV, 600mV, 620mV, 640mV, 660mV, 680mV or 700mV etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value is equally applicable.

Current potential in the present invention is the current potential relative to standard hydrogen electrode, in the potential range, the life of ihleite precipitating At greatly reducing, the passivation in chalcopyrite at lixiviating course is reduced, to promote the leaching of chalcopyrite.

Preferably, when the current potential of the Bioleaching system is more than 700mV, medicament is supplemented into Bioleaching system.

As currently preferred technical solution, the partial size of chalcopyrite ore is P in the microorganism dump leaching system₈₀> 5mm, such as 5.1mm, 10mm, 20mm, 30mm, 40mm, 50mm, 70mm or 100mm etc., it is not limited to cited number Value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 5~50mm.

Preferably, the partial size of chalcopyrite ore is P in the microorganism leaching system₈₀≤ 5mm, such as 5mm, 3mm, 1mm, 0.75mm, 0.5mm, 0.25mm, 0.1mm, 0.08mm, 0.05mm, 0.02mm or 0.01mm etc., it is not limited to listed The numerical value of act, other interior unlisted numerical value of the numberical range are equally applicable, preferably 0.02~1mm.

In the present invention, P₈₀Refer to the 80% attainable granularity of particle, P₈₀> 5mm shows the grain for having 80% particle Diameter is greater than 5mm, and P₈₀≤ 5mm then shows have the partial size of 80% particle no more than 5mm.

As currently preferred technical solution, the extracting solution is sulfuric acid and ferric mixed solution.

Preferably, sulfuric acid concentration is 0.1~20g/L, such as 0.1g/L, 0.2g/L, 0.5g/L, 1g/ in the extracting solution L, 2g/L, 5g/L, 10g/L, 15g/L or 20g/L etc., it is not limited to cited numerical value, in the numberical range, other are not The numerical value enumerated is equally applicable, preferably 5~15g/L.

Preferably, ferric iron concentration is 0.1~50g/L, such as 0.1g/L, 0.5g/L, 1g/L, 5g/ in the extracting solution L, 10g/L, 20g/L, 30g/L, 40g/L or 50g/L etc., it is not limited to cited numerical value, in the numberical range other Unlisted numerical value is equally applicable, preferably 5~20g/L.

As currently preferred technical solution, the microorganism includes acidophilic microorganism.

Preferably, the acidophilic microorganism include Leptospirillum, Thiobacillus, irony Pseudomonas, Sulfobacillus or Sour germ belong in any one or at least two combination, the combination typical case but non-limiting example has: Leptospirillum With the combination of Thiobacillus, the combination of irony Pseudomonas and Sulfobacillus, the combination that irony Pseudomonas and sour germ belong to, Thiobacillus Category, irony Pseudomonas and combination of Sulfobacillus etc..

Preferably, the acidophilic microorganism includes any one in iron-oxidizing bacteria, sulfur oxidizing bacterium or iron sulfur oxidizing bacterium or extremely Few two kinds of combination, the combination is typical but non-limiting example has: the combination of iron-oxidizing bacteria and sulfur oxidizing bacterium, sulfur oxidizing bacterium with The combination of iron sulfur oxidizing bacterium, iron-oxidizing bacteria, sulfur oxidizing bacterium and combination of iron sulfur oxidizing bacterium etc..

Preferably, it acidophilic microorganism inoculation or is grown in the ore of Bioleaching system naturally or Bioleaching body In the extracting solution of system.

Preferably, the acidophilic microorganism in ore, tailing, extracting solution or the acidic mine water any one or at least Two kinds of combination, the combination is typical but non-limiting example has: the combination of the combination of ore and tailing, tailing and extracting solution, The combination of extracting solution and acidic mine water, ore, tailing and combination of extracting solution etc..

As currently preferred technical solution, the Adding Way of the medicament includes directly and in Bioleaching system Ore is mixed and/or is dissolved in the extracting solution of Bioleaching system.

Preferably, when the medicament is directly mixed with the ore in Bioleaching system, the usage amount of the medicament is 5 ~1000mg/kg ore, such as 5mg/kg ore, 10mg/kg ore, 30mg/kg ore, 50mg/kg ore, 100mg/kg mine Stone, 200mg/kg ore, 500mg/kg ore, 800mg/kg ore or 1000mg/kg ore etc., it is not limited to cited Numerical value, other unlisted numerical value are equally applicable in the numberical range, preferably 10~100mg/kg ore.

Preferably, when the medicament dissolution is in the extracting solution of Bioleaching system, the usage amount of the medicament is 20 ~5000mg/L extracting solution, for example, 20mg/L extracting solution, 50mg/L extracting solution, 100mg/L extracting solution, 200mg/L extracting solution, 500mg/L extracting solution, 1000mg/L extracting solution, 2000mg/L extracting solution, 3000mg/L extracting solution, 4000mg/L extracting solution or 5000mg/L extracting solution etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable With preferably 50~500mg/L extracting solution.

As currently preferred technical solution, the extracting solution in the Bioleaching system is extracted, obtained extraction Extraction raffinate is recycled as extracting solution.

In the present invention, the infusion solution that the extracting solution Chalcopyrite Leaching is formed, after extraction electrodeposition obtains copper, raffinate Liquid can be returned to be recycled as extractant.

As currently preferred technical solution, the method are as follows: medicament is added into chalcopyrite Bioleaching system, makes The current potential for obtaining the Bioleaching system is maintained 580~700mV, when the current potential of the Bioleaching system is more than 700mV, Medicament is supplemented into Bioleaching system；

The Bioleaching system includes chalcopyrite ore, extracting solution and acidophilic microorganism, using microorganism dump leaching system When, the partial size of chalcopyrite ore is P₈₀> 5mm, when using microorganism leaching system, the partial size of chalcopyrite ore is P₈₀≤ 5mm, the extracting solution are sulfuric acid and ferric mixed solution, and the sulfuric acid concentration is 0.1~20g/L, and ferric iron concentration is 0.1~50g/L, acidophilic microorganism inoculation or is grown in the ore of Bioleaching system or Bioleaching system naturally In extracting solution；

The medicament includes surfactant and/or isothiazolinone biocide agent, and the Adding Way of the medicament includes It directly mixes and/or is dissolved in the extracting solution of Bioleaching system with the ore in Bioleaching system, when the medicament is straight It connects when being mixed with the ore in Bioleaching system, the usage amount of medicament is 5~1000mg/kg ore, when the medicament dissolution When in the extracting solution of Bioleaching system, the usage amount of medicament is 20~5000mg/L extracting solution.

Compared with prior art, the invention has the following advantages:

The present invention is by the addition ferrous activity of agent modulates microbiological oxidation, to regulate and control the electricity of Bioleaching system Position reduces the formation of passivating film in chalcopyrite at lixiviating course, promotes the leaching of chalcopyrite, compared with when being not added with medicament, brass The leaching rate of mine can be improved 0.7~2.8 times, and leaching rate improves 2~3 times.

Detailed description of the invention

Fig. 1 is change curve of the embodiment of the present invention 7 with Leaching Systems current potential in comparative example 2 with extraction time；

Fig. 2 is change curve of the embodiment of the present invention 8 with leaching of copper pyrites extracting rate in comparative example 3 with extraction time.

Specific embodiment

In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this Invention protection scope is subject to claims.

Specific embodiment of the invention part provides a kind of method of chalcopyrite Bioleaching, the method are as follows: to Huang Medicament is added in copper mine Bioleaching system, the medicament includes surfactant and/or isothiazolinone biocide agent.

The following are typical but non-limiting embodiments of the invention: