WO2012055167A1

WO2012055167A1 - Bacterial liquid of microbial combinations for biometallurgical leaching of copper ore and method for recovering metallic copper therefrom

Info

Publication number: WO2012055167A1
Application number: PCT/CN2011/001790
Authority: WO
Inventors: 邱冠周; 覃文庆; 刘学端; 王军; 尹华群; 刘新星; 周洪波; 康健; 余润兰; 申丽; 张雁生; 曾伟民; 朱德庆; 李启厚; 庄田
Original assignee: 中南大学
Priority date: 2010-10-31
Filing date: 2011-10-26
Publication date: 2012-05-03
Also published as: CN101956071A; CN101956071B

Abstract

Disclosed is a bacterial liquid of microbial combinations for biometallurgical leaching of copper ore and a method for recovering metallic copper therefrom. A microbial leaching combination, after undergoing adaptive culture, continuous amplification culture and ore heap adaptive culture, is used for leaching, with different leaching methods being applied for different ore types, these methods comprising biometallurgical processing methods for lump ore, ore fines, ore tailings and copper smelting-furnace slag. The standard leachate so obtained renders two products, being subjected to extraction-electrotwinning to obtain cathode copper and to short-process replacement to obtain sponge copper. The method is suitable for industrial production under different conditions while enabling high-efficiency exploitation of low-grade copper ores and protection of the ecological environment of mining areas, thus being favorable for economic and environmental reasons.

Description

Biometallurgical leaching microorganism combined bacteria liquid of copper ore and method for recovering same

The invention belongs to the field of biometallurgy, and particularly relates to a biometallurgical leaching microbial combined bacterial liquid of copper ore and a method for recovering copper metal.

Background technique

Copper is an important strategic non-ferrous metal used in electrical, mechanical, and defense industries. The world's copper resources are mainly concentrated in Chile, the United States, Zambia and other countries. Zambia's copper reserves account for 6.4% of the global total, but among the proven copper resources, a considerable number of copper mines have yet to be developed due to the lack of efficient use of new technologies. In particular, the large amount of tailings and mining waste rock resources in the Zambian countries require a large amount of government funds to maintain the waste rock piles. However, due to the lack of effective technology, a large amount of heavy metal-containing wastewater is generated during the ore storage process, which is not effective. Recycling heavy metal elements, and causing tremendous damage to the ecosystem, causing serious pollution to the mining environment.

Biometallurgy is the use of mineral-based micro-organisms to oxidize and decompose minerals to allow metal ions to enter the solution, further separating and extracting metals. It has the characteristics of short process, low cost, environmental friendliness and low pollution. Especially microbial metallurgy technology can deal with low-grade, complex and difficult-to-handle mineral resources, with advanced technology and high production efficiency. At present, the global production of metal copper by biometallurgical technology has accounted for 25% of total copper production, and the United States and Chile have even reached 30%.

There are three main types of biometallurgical processes: heap leaching, in situ leaching and agitation leaching. The choice of process is based on the type of ore and the physicochemical properties of the mineral components. The ores currently involved are: copper ore, nickel-cobalt ore, gold and uranium. However, there is currently no complete and appropriate treatment method for various grades of oxidized ore and sulfide ore type copper ore and smelting slag and mining waste rock.

Summary of the invention

The object of the present invention is to provide a copper ore of various grades of oxidized ore and sulfide ore, including lump ore, fine ore, tailings, acid massive waste rock, by utilizing a mixture of a plurality of invading microorganisms. The biometallurgical treatment methods of copper smelting furnace slag, etc., are suitable for industrial production under different conditions, realizing efficient use of resources, effectively protecting the ecological environment of the mining area, and achieving a win-win situation of economic benefits and environmental friendliness.

The invention relates to a biometallurgical leaching microbial combined bacterial liquid of copper ore, which is a mixture of microorganisms required for leaching after adaptive cultivation, continuous expansion culture and adaptive cultivation of ore piles, and the concentration is l-8xl0 ⁶ cdl. /mL mixed bacterial solution, the mixed bacterial liquid is combined according to the cell concentration ratio per unit volume: Thiobacillus ferrooxidans 30 ± 5.0%, Thiobacillus acidophilus 15 ± 3.0%, ferrous oxide Leptospirillum 30 ± 5.0%, Thiobacillus thermophilus 12 3.0%, mesophilic sulfur-oxidized sulphide 3 ± 0.5%, metal sulphate 2 ± 0.5%, diligent metalococcus 3 ± 0.5%, acidophilus 3 ± 0.5%, Phytophthora 2 ± 0.5% _; The acidophilic Thiobacillus ferrooxidans has 16 deposit numbers as CCTCC AB 206199, CCTCC AB 206200, CCTCC AB 206201, CCTCC AB 206202, CCTCC AB 206203, CCTCC AB 206204 > CCTCC AB 206205, CCTCC AB 206206, CCTCC AB 206207, One or more of CCTCC AB 206208, CCTCC AB 207053, CCTCC AB 207054, CCTCC AB 207055, CCTCC AB 207056, CCTCC AB 207057, CCTCC AB 207058; Thiobacillus acidophilus is the three deposit numbers CCTCC AB206195, CCTCC One or more of AB 206196 and CCTCC AB 206197; Leptospirillum oxidizing bacteria are 10 kinds of accession numbers are CCTCC AB206158, CCTCC AB 206159, CCTCC AB 206160, CCTCC AB 206161, CCTCC AB 206162, CCTCC AB 206163, CCTCC One or more of AB 206164, CCTCC AB 207036, CCTCC AB 207037, CCTCC AB 207038; Thiobacillus thermophilum is one of three types of CCTCC AB207044, CCTCC AB 206175, CCTCC AB 206176 or Several types; mesophilic sulfur-oxidized sulphide CCTCC AB207045, metal sulphate CCTCC AB207047, metal sulphate are one or more of three kinds of accession numbers CCTCC AB207046, CCTCC AB 206191, CCTCC AB 206192; acidophilus is 14 The accession numbers are CCTCC AB206219, CCTCC AB 206220, CCTCC AB 20622 K CCTCC AB 206222, CCTCC AB 206223, CCTCC AB 206224, CCTCC AB 206225, CCTCC AB 206226, CCTCC AB 207065, CCTCC AB 207066, CCTCC AB 207067, CCTCC AB 207068 , CCTCC AB 207069, CCTCC AB 207070 one or several; Phytophthora CTCCC AB207048.

The ore heap adaptive culture is to add -0.074 mm of 2-5% w/v copper ore or concentrate as a mixed medium in the chemical medium; after the microbial concentration reaches at least l-8x10 ⁷ cell/mL Then inoculate the 5-10 tons of ore heap according to l-8xl0 ⁶ cell/mL, and carry out the adaptive growth of the ore heap, so that it is in the logarithmic growth phase. After the microbial concentration reaches at least l-8x10 ⁶ cell/mL, press l -8xl0 ⁰ cell/mL was inoculated into a 100-500 ton ore heap for 20-40 days.

The method for biometallurgical recovery of copper ore by using the leaching microorganism combined bacteria liquid comprises the following steps -

(1) Block ore biolead

Laying the bottom layer and the anti-seepage layer, and pre-cracking the +5-40mm grain-level copper ore large particle lump with a thickness of 200-300mm on the anti-seepage layer as the buffer layer of the yard; continue to be broken. +5-40mm grain size copper ore large particle lump ore is deposited in a thin layer, pre-sprayed with dilute sulfuric acid solution, and then inoculated with the leaching microorganism combination liquid solution according to l-8x10 ⁶ cell/mL, and intermittent spraying is started. Leach production operations and ventilation, leaching solution standby;

(2) Powder ore mixing bacteria biological tank dip

Adding a crushed -5mm-grained copper ore fine ore and concentrated sulfuric acid, containing the combined leaching microorganisms Stir the tank so that the concentration of microorganisms in the mixed solution is l-8x l0 ⁶ cdl/mL; stir leaching in a stirred tank, and the leaching solution is reserved;

(3) Tailings granulation biopsy

Firstly, the copper ore tailings are pelletized and granulated, the particle size is controlled at 10-20mm, 150-200mm thick copper ore fines with a particle size of 5mm are laid as the bottom layer, and the anti-seepage layer is laid, and the anti-seepage layer is laid flat 200 - 300mm thick grit, as a buffer layer of the yard; then, on the buffer layer, the pelletized copper ore tailings with a particle size of 10-20mm after pelletizing and granulation are laid and piled up. Spraying in advance, and then inoculating the combined leaching microorganisms, the microbial concentration is l-8×10 ⁶ cells/mL, intermittent spraying, and the leaching solution is reserved;

(4) Powder ore and acid block waste rock bioreactor

The copper ore mining acidic massive waste rock with a particle size of 40mm-60mm with a copper content of 0.09-0.3% is laid as the bottom layer, and the thickness is 300-400mm; the anti-seepage layer is covered, and the anti-seepage layer is flat-stacked 200-300mm thick. The copper ore fines with a particle size of 5mm, as a buffer layer of the yard, the multi-layer laying method of the ore heap, first laying the first layer of copper ore acidic massive waste rock, using a mortar pump to pump copper with a mass concentration of 30% The tailings sand pump is pumped onto the waste rock layer, so that the tailings can be evenly and firmly distributed in the ore layer; the second layer of waste rock layer is laid and the tailings sand is pumped; so repeatedly, until the pile height of each layer of the pile is 4- 6M; pre-spraying of sulfuric acid in the early stage of heap leaching, and then inoculating the leaching microorganism combined bacteria solution, the microbial concentration is l -8×10 ⁶ cell/mL, intermittent spraying, and the leaching solution is reserved;

(5) Pulverized ore and finely ground copper smelting furnace slag granulation bio-drap

Firstly, the copper smelting furnace slag is crushed and finely ground, and then granulated with the powder ore. The particle size is controlled at 20mm, and the 150-200mm thick powder with a particle size of 5mm is used as the bottom layer, and the upper layer is covered with the anti-seepage layer. The finely ground smelting slag and powder ore of 200-300min thickness are formed on the top of the infiltration layer as a buffer layer of the yard; then the heap leaching of the finely ground smelting slag and the fine ore by the pelletizing granulation is continued Pre-spraying of sulfuric acid in the early stage of heap leaching, and then inoculating the leaching microorganism combined bacteria solution, the microbial concentration is l-8x l 0 ⁶ cell/mL, intermittent spraying, and the leaching solution is reserved;

(6) extracting one or more of the leachate obtained by the above steps (1) - (5) by electrowinning to prepare electric copper; or using one or more of the leachate obtained by the above steps (1) - (5) Replacement to obtain sponge copper.

In the lump ore biopile immersion according to the step (1), the bottom layer is a coarse sand having a thickness of 300-400 mm, and the crushed copper ore of a grade of 5-40 mm is subjected to thin layer pile-up, each Layer height 5-7m, laying 4-6 layers; first spray with dilute sulfuric acid solution with pH value of 0.9-1.2, ensure that the pH value of the leachate is maintained at 1.7-1.9, and the pH value of the leachate is stable for 48 hours, inoculate the above The leaching microorganism combines the bacterial liquid.

The mass concentration of sulfuric acid in the mixed solution in the stirred tank in the powder ore mixing bacteria biological tank immersion according to the step (2) It is 30-45g/L; the stirring speed is 40-60 rpm; during the stirring process, air can be blown into the stirring tank by air compressor, and the reaction is leached for 1-3 hours.

In the tailings granulation biological heap leaching described in the step (3), 2% dilute sulfuric acid is added during the granulation, the particle size is controlled at 20 mm, and the sulfuric acid is pre-sprayed in the early stage of the heap leaching to ensure that the leaching environment pH is maintained at the same time. 1.7-1.9, the pH was stable for 24 hours, and the leaching microorganism combined bacteria solution was inoculated.

In the dust leaching of the powder ore and acid massive waste rock in the step (4), the pre-spraying of the sulfuric acid is carried out in advance, to ensure that the pH of the leaching environment is maintained at 1.7-1.9, and the pH of the environment is stable for 24 hours. The inoculation of the leaching microorganism combined bacteria solution is performed.

In the powder ore and fine grinding copper smelting furnace slag granulation biological heap leaching described in the step (5), when the pulverized ore and the fine grinding copper smelting furnace slag are granulated, the copper smelting furnace slag is firstly crushed and finely ground to make it -0.074 The content of mm is not less than 50%, and it is granulated by using 35-40g/L sulfuric acid. After granulation, it is left open for 8-12 hours to stabilize the surface of the solidified ball; Pre-spraying, ensuring that the pH of the leaching environment is maintained at 1.7-1.9, and the immersion microbial combined bacteria solution is inoculated after the environmental pH value is stable for 24 hours.

Step (1) (3) (4) (5) The anti-seepage layer is an acid-resistant PVC geotextile with a thickness of lmm-3inin. The specific process for extracting electrowinning copper prepared by the step (6) is as follows: the extraction adopts two-stage extraction first-stage back extraction; using Lix-984 as an extracting agent, the leaching liquid is first injected into the high-level tank of the extraction raw liquid, and the organic phase high-position tank The extractant in the extraction is fed into the extraction tank two-stage extraction according to 0/A 1:1, and the residual liquid flows to the circulation tank after the extraction, and the pump is returned to the ore heap to continue to utilize the leaching; the organic phase and the stripping agent are extracted by the first stage. After stripping, the no-load organic phase is returned to reuse; the residual liquid and the electro-remaining liquid are subjected to full closed-circuit recycling; the electrowinning is performed by the Isa method; after the stripping, the liquid is filtered to self-flow to the electro-hydraulic circulation tank, via the plate type. After the heat exchanger is heated to 40-42 ° C, it flows into the electric accumulator to accumulate, and the electrolyzed lean liquid returns as the stripping agent; the cathode working period is 7 days, the cathode copper is manually stripped; the anode mud is washed once a year, with the movement The pump is pumped away from the tank.

The specific process for obtaining the sponge copper according to the step (6) is as follows: the initial pH value of the leachate is adjusted to be between 1.5 and 2.0, and the Fe ^{3+ is} removed before the replacement, and the Fe ³⁺ concentration is controlled to be not higher than 0.2 g/L; The pH value is controlled below 4.5; the stirring strength is 100~150 ipm/s _{; the} room temperature is replaced, and the replacement time is 30 min.

By using the present invention, various types of copper ore, including sulfide ore and oxidized ore, whether it is mining waste rock or beneficiation tailings, including smelted waste, can be treated by this technology, and various resources can be made. In addition, the application of biometallurgical technology is beneficial to the effective utilization of tailings heap resources and the effective recovery of valuable copper metal, which can well protect the ecological environment of the mining area and achieve a win-win situation of economic benefits and environmental friendliness.

Advantages and positive effects of the invention

The key to the invention lies in the copper ore, mining waste rock, beneficiation tailings, and slag after smelting for different objects. By utilizing each adaptive process, resources can be fully utilized. The recovery rate of the bio-stacking process is over 90%, and the recovery rate of the bio-stirring leaching process is more than 90%. The obtained leachate can obtain high-quality cathode electro-copper products through the extraction electrowinning process, and the sponge copper can be obtained through the replacement process.

The invention has broad promotion value and application prospect in the copper ore hydrometallurgy industry all over the world, and can broaden the source of raw materials, increase resource reserves, reduce production cost, improve resource utilization efficiency, and extend mine service life.

detailed description

The invention is further illustrated by the following examples, without limiting the invention.

The application of new biometallurgical technology in the Chambishi copper mine in Zambia is shown in Table 1. The analysis results of the cultured microbial community are shown in Table 2.

Table 1 Chemical multi-element analysis of low-grade ore, %

Fe Cu Co Ni s Si0 ₂ A1 ₂ 0 ₃ CaO MgO

4.07 2.07 0.03 0.0035 0.40 58.32 11.21 1.12 3.44 Example 1

5.62 4.56 0.023 0.0021 0.69 65.21 9.63 2.35 2.65 Example 2

6.93 2.01 0.021 0.0025 0.81 59.38 10.28 3.01 1.96 Example 3

5.98 2.11 0.025 0.0031 1.21 63.25 12.31 1.56 1.62 Example 4

Table 2 Cell volume concentration composition per unit volume of mixed bacteria, % eosinate ferrous oxide, acidophilic sulphur oxide, ferrous oxide hook, mesophilic sulfur oxidation, metal thermophilic sulfur bacterium

Thiobacillus brevis, Helicobacter pylori

27.25 15.36 30.21 12.25 3.33 2.46 Metaliscus of diligence Acidophilic bacteria

3.35 3.48 2.31

The above strains were purchased at the China National Type Culture Collection (CCTCC) Biometallurgical Species Resource Bank.

The acidophilic Thiobacillus ferrooxidans has 16 deposit numbers as CCTCC AB 206199 CTCC AB 206200, CCTCC AB 206201, CCTCC AB 206202, CCTCC AB 206203, CCTCC AB 206204, CCTCC AB 206205, CCTCC AB 206206, CCTCC AB 206207 , one or more of CCTCC AB 206208, CCTCC AB 207053, CCTCC AB 207054, CCTCC AB 207055, CCTCC AB 207056, CCTCC AB 207057, CCTCC AB 207058; the acidophilic Thiobacillus thiooxidans is the three deposit numbers CCTCC AB206195, One or more of CCTCC AB 206196 and CCTCC AB 206197; Leptospirillum oxidizing bacteria are 10 kinds of accession numbers are CCTCC AB206158 CTCC AB 206159, CCTCC AB 206160, CCTCC AB 206161, One or more of CCTCC AB 206162, CCTCC AB 206163, CCTCC AB 206164, CCTCC AB 207036, CCTCC AB 207037, CCTCC AB 207038; Thiobacillus thermophilum is the three deposit numbers CCTCC AB207044, CCTCC AB 206175, CCTCC AB 206176 One or more of the thermophilic sulfur-oxidized S. sulphide CCTCC AB207045, the metal sulfur leaf fungus CCTCC AB207047, and the three species of C. sinensis are CCTCC AB207046, CCTCC AB 206191, CCTCC AB 206192; Acid bacteria are 14 kinds of deposit numbers as CCTCC AB206219, CCTCC AB 206220, CCTCC AB 20622 CCTCC AB 206222, CCTCC AB 206223, CCTCC AB 206224, CCTCC AB 206225, CCTCC AB 206226, CCTCC AB 207065, CCTCC AB 207066, CCTCC AB 207067, One or more of CCTCC AB 207068, CCTCC AB 207069, CCTCC AB 207070; C. sinensis CCTCC AB207048.

The names of the above strains are as follows:

CCTCC AB 206199 Thiobacillus ferrooxidans CSU 206059 Acidithiobacillus ferrooxidans CCTCC AB 206200 Thiobacillus ferrooxidans CSU Acidithiobacillus ferrooxidans

CCTCC AB 206201 Thiobacillus ferrooxidans CSU 206062 Acidithiobacillus ferrooxidans CCTCC AB 206202 Thiobacillus ferrooxidans CSU i 6 Acidithiobacillus ferrooxidans CCTCC AB 206203 Thiobacillus ferrooxidans CSU 206065 Acidithiobacillus ferrooxidans CCTCC AB 206204 Acidophilus Thiobacillus ferrooxidans CSU 206066 Acidithiobacillus ferrooxidans CCTCC AB 206205 Thiobacillus ferrooxidans CSU 206068 Acidithiobacillus ferrooxidans CCTCC AB 206206 Thiobacillus ferrooxidans CSU 2ΰβ0β9 Acidithiobacillus ferrooxidans CCTCC AB 206207 Thiobacillus acidophilus CSU 206071 Acidithiobacillus ferrooxidans CCTCC AB 206208 Thiobacillus ferrooxidans CSU 206073 Acidithiobacillus ferrooxidans CCTCC AB 207053 Thiobacillus ferrooxidans CSU 206061 Acidithiobacillus ferrooxidans CCTCC AB 207054 Thiobacillus ferrooxidans CSU 206063 Acidithiobacillus ferrooxidans CCTCC AB 207055 Acidophilic ferrous oxide Bacillus CSU 20606Ί Acidithiobacillus ferrooxidans CCTCC AB 207056 Thiobacillus ferrooxidans CSU 206Q10 Acidithiob Acillus ferrooxidans CCTCC AB 207057 Thiobacillus ferrooxidans CSU 206072 Acidithiobacillus ferrooxidans CCTCC AB 207058 Thiobacillus ferrooxidans CSU 2060Ί Acidithiobacillus ferrooxidans

CCTCC AB206195 Thiobacillus acidophilus CSU 206051 Acidithiobacillus thiooxidans CCTCC AB 206196 Thiobacillus acidophilus CSU 206052 Acidithiobacillus thiooxidans CCTCC AB 206197 Thiobacillus acidophilus CSU 206053 Acidithiobacillus thiooxidans CCTCC AB206158 Leptospirillum CSU 206002 Leptospirillum ferrooxidans CCTCC AB206159 Leptospirillum CSU 206003 Leptospirillum ferrooxidans CCTCC AB206160 Leptospirillum CSU 206004 Leptospirillum ferrooxidans CCTCC AB206161 Leptospirillum CSU 206005 Leptospirillum ferrooxidans CCTCC AB206162 Leptospirillum CSU 206006 Leptospirillum ferrooxidans CCTCC AB206163 Leptospirillum CSU 206008 Leptospirillum ferrooxidans CCTCC AB206164 Leptospirillum CSU 206009 Leptospirillum ferrooxidans CCTCC AB207036 Leptospirillum CSU 206001 Leptospirillum ferrooxidans CCTCC AB207037 Leptospirillum CSU 206007 Leptospirillum ferrooxidans CCTCC AB207038 Leptospirillum CSU 206010 Leptospirillum ferrooxidans

CCTCC AB 207044 Thiobacillus thermophilus CSU206027 Acidithiobacillus caldus

CCTCC AB 206175 Thiobacillus thermophilus CSU206026 4c/i3⁄4 o6crd//ws caldus

CCTCC AB 206176 Thiobacillus thermophilus CSU206028 Acidithiobacillus caldus

CCTCC AB207045 mesophilic sulfur-oxidized sulphate CSU 206 A3Sulfobacillus thermosulfidooxidans CCTCC AB207047 metal sulphate CSU 206047 Sulfolobus metallicus

CCTCC AB207046 Diligent Metalococcus CSU 206045 Metallosphaera sedula

CCTCC AB206191 Diligent Metalococcus CSU 206044 Metallosphaera sedula

CCTCC AB206192 Diligent Metalococcus CSU 206046 Metallosphaera sedula

CCTCC AB206219 Acidophilus CSU 206091 Acidiphilium sp.

CCTCC AB206220 Acidophilus CSU 206093 Acidiphilium sp.

CCTCC AB206221 Acidophilus CSU 206094 Acidiphilium sp.

CCTCC AB206222 Acidophilus CSU 206096 Acidiphilium sp.

CCTCC AB206223 Acidophilus CSU 206097 Acidiphilium sp.

CCTCC AB206224 Acidophilus CSU 206099 Acidiphilium sp.

CCTCC AB206225 Acidophilus CSU 206101 Acidiphilium sp.

CCTCC AB206226 Acidophilus CSU 206103 Acidiphilium sp. CCTCC AB 207065 Acidophilus CSU 206092 Acidiphilium sp.

CCTCC AB 207066 Acidophilus CSU 206095 Acidiphilium sp.

CCTCC AB 207067 Acidophilus CSU 206098 Acidiphilium sp.

CCTCC AB 207068 Acidophilus CSU 206100 Acidiphilium sp.

CCTCC AB 207069 Acidophilus CSU 206102 Acidiphilium sp.

CCTCC AB 207070 Acidophilus CSU 206104 Acidiphilium sp.

CCTCC AB207048 million acid bacteria CSU 206050Acidianus manzae is.

The specific process is as follows:

Firstly, the microorganisms required for leaching were separately cultured in 2.5L shake flasks, and the corresponding chemical medium of each microorganism was used. After each microorganism was successively passaged five times, it was inoculated into the corresponding 50L continuous expansion culture device, using the ore. concentrate for mixing powder and medium; the microorganism concentration of at least ^{_{l-8xl0 7 C ell / mL}} , and then seeded to 5-10 tons of ore heap, stockpile for adaptive growth, it is in the logarithmic growth phase, the microorganism After the concentration reaches at least l-8x10 ⁶ cell/mL, it is inoculated into 100-500 tons of ore heap. After 20-40 days, the microorganisms required for leaching in the ore heap are combined in the expanded culture medium according to the above table:

Example 1

Block ore heap leaching:

Laying the bottom layer and the anti-seepage layer, the bottom layer is 300-400mm grit coarse sand, and the pre-crushed +5-40mm grain-level copper ore large grain lump ore with a thickness of 200-300mm is piled on the anti-seepage layer as a pile. The buffer layer of the field; successively, the crushed +5-40mm grain copper ore large grain lump ore is piled up in thin layers, the height of each layer is 5-7m, laying 4-6 layers; firstly, the pH value is 0.9. Pre-spraying of -1.2 dilute sulfuric acid solution to ensure the pH value of the leachate is maintained at 1.7-1.9. After the pH value of the leachate is stable for 48 hours, inoculate the above-mentioned leaching microorganism combination according to l-8x10 ⁶ cell/mL, and start intermittent spray production operation and Ventilation, heap immersion for 270 days, copper leaching rate of 90.11%, obtaining a copper ion concentration of 2.51g / L of leachate.

Powder ore bacteria agitation leaching:

Adding the crushed -5mm grain copper ore fine ore and concentrated sulfuric acid, and the above-mentioned leaching microorganism combination to the stirring tank, the liquid solid product mass ratio is 2.33L/kg, so that the microbial concentration in the mixed solution is l-8xl0 ⁶ Cell/mL _{; the} concentration of sulfuric acid in the mixed solution in the stirred tank is 30-45g/L _{; the} volume of the stirred tank is 50M ³ , the temperature is stirred and leached for 2 hours at room temperature, the stirring speed is 60 rpm, and the average of one month of continuous operation The process indicators are: copper leaching rate of 92.32%, sulfuric acid consumption of 3.18 tons / ton of copper, obtaining a copper ion concentration of 4.85 g / L of leachate. The two parts of the leachate were mixed for extraction and electrowinning, and the first batch of cathode copper with a purity of 99.995% was obtained. The specific process of extracting electrowinning copper is as follows. The extraction adopts two-stage extraction first-stage back extraction; using Lix-984 as an extractant, the leachate is first injected into the high level tank of the extraction stock solution, compared with the extractant in the organic phase clamping tank. 0/A 1 :1 Self-flowing into the extraction tank for two-stage extraction, after the extraction, the residual liquid flows to the circulation tank, and the pump returns to the ore heap to continue to use the leaching; the extracted organic phase and the stripping agent are subjected to the first-stage stripping, and the organic The phase is returned to reuse; the residual liquid and the electro-remaining liquid are subjected to full closed-circuit recycling; the electrowinning is performed by the Isa method; after the stripping, the liquid is filtered to self-flow to the electro-hydraulic circulation tank, and is heated to 40 by the plate heat exchanger. After -42, it flows into the electric accumulator to carry out electrowinning, and the electrolyzed lean liquid returns as a stripping agent; the cathode working cycle is 7 days, and the cathode copper is manually stripped; the anode mud is washed once a year, and is removed from the tank by a moving pump.

Example 2

According to the operation of the block lump of Example 1, for 270 days, the leaching rate of copper was 94.23%, and a leachate having a copper ion concentration of 3.66 g/L was obtained.

According to the operation of Example 1, the powdery ore bacteria were stirred, and the average process index for one month of continuous operation was: copper leaching rate was 95.62%, sulfuric acid consumption was 3.65 tons/ton of copper, and a copper ion concentration of 5.78 g/L of leachate was obtained. The two parts of the leachate were mixed for extraction and electrowinning, and the first batch of cathode copper with a purity of 99.995% was obtained.

Example 3

According to the operation of the embodiment 1, the heap leaching was carried out for 270 days, and the leaching rate of copper was 90.25%, and a leachate having a copper ion concentration of 2.45 g/L was obtained.

According to the operation of Example 1, the powdery ore bacteria were stirred, and the average process index for one month of continuous operation was as follows: copper leaching rate was 92.32%, sulfuric acid consumption was 3.25 tons/ton of copper, and a copper ion concentration of 4.75 g/L of leachate was obtained. The two parts of the leaching solution were mixed for extraction and electrowinning, and the first batch of cathode copper with a purity of 99.995% was obtained. A portion of the leachate was obtained by a displacement process to obtain 88% copper sponge copper.

The specific process for obtaining sponge copper is as follows: the initial pH value of the leachate is adjusted to be between 1.5 and 2.0, and Fe ^{3+ is} removed before the replacement, and the Fe ³⁺ concentration is not higher than 0.2 g/L _{; the} replacement end point is that the pH is controlled below 4.5. The stirring strength is 100~150rpm/s _{; the} normal temperature is replaced, and the replacement time is 30min.

Example 4

According to the operation of the block lump of Example 1, for 270 days, the leaching rate of copper was 91.24%, and a leachate having a copper ion concentration of 2.68 g/L was obtained.

According to the operation of Example 1, the powdery ore bacteria were stirred, and the average process index for one month of continuous operation was: copper leaching rate was 92.32%, sulfuric acid consumption was 3.36 tons/ton of copper, and a copper ion concentration of 4.97 g/L of leachate was obtained. A part of the two parts of the leachate was mixed for extraction and electrowinning, and the first batch of cathode copper with a purity of 99.995% was obtained. A portion of the leachate was obtained by a displacement process to obtain 88% copper sponge copper. Example 5

Table 3 Chemical multi-element analysis of copper mining waste rock, %

Fe Cu Co Ni S Si0 ₂ A1 ₂ 0 ₃ CaO MgO

6.12 0.87 0.02 6.05 Example 5

Table 4 Chemical multi-element analysis of copper smelting waste residue, %

Fe Cu Co Cr S Si0 ₂ Al CaO MgO

p

54.07 2.35 0.43 0.015 0.61 23.55 1.02 0.11 0.75 Example 5 Powder ore and acid block waste rock bio-dip immersion: to

Laying 300-400mm copper ore mining acid block-like waste rock with 0.09-0.30% copper as the bottom layer, and then covering the anti-seepage layer, and stacking 200-300mm thick copper ore powder with a particle size of 5mm on the anti-seepage layer. Mine, as the buffer layer of the yard, the pile is to be multi-layered. First, the first layer of copper ore acid block waste rock is laid, and the copper mine tailings with a mass concentration of 30% are pumped to the waste rock layer with a mortar pump. The tailings can be evenly and firmly distributed in the ore layer; the second layer of waste rock layer is laid and the tailings sand is pumped; this is repeated until the pile height of each layer of the pile is 4-6M; The pre-spraying of sulfuric acid is carried out to ensure that the pH of the leaching environment is maintained at 1.7-1.9, and the pH of the environment is stabilized for 24 hours, and then the above-mentioned leaching microorganism combination inoculation is carried out, and the microbial concentration is l- ⁸ ×10 ⁶ cdI/mL, and intermittent spraying is performed. Leaching, leaching solution;

Powder ore and fine grinding copper smelting furnace slag granulation bio-dumping:

When slag granulation of fine ore and fine grinding copper smelting furnace, the copper smelting furnace slag is firstly crushed and finely ground, so that the content of -0.074mm is more than 50%, and the sulfuric acid is -0.074mm by 35-40g/L. Grade content of more than 70% of powdered ore and finely ground copper smelting slag for pelletizing and granulation, after granulation, open for 8-12 hours to stabilize the surface of the solidified ball; pre-spraying of sulfuric acid in the early stage of heap leaching to ensure leaching The pH of the environment was maintained at 1.7-1.9, and the environmental pH value was stabilized for 24 hours. The above-mentioned leaching microorganism combination inoculation was carried out, and the microbial concentration was l-8×10 ⁰ cell/mL, intermittent spraying was performed, and the leachate was reserved.

The above-mentioned fine ore and acid massive waste rock, fine ore and finely ground copper smelting slag were all immersed for 270 days, and the copper leaching rate was 85.24%, and a copper ion concentration of 1.65 g/L was obtained. The leachate was mixed for extraction and electrowinning, and the first batch of cathode copper was obtained with a purity of 99.95%. A part of the sponge copper containing 87% of copper was obtained by a displacement process.

Claims

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The invention relates to a biometallurgical leaching microbial combined bacterial liquid of copper ore, which is characterized in that the microorganisms required for leaching after adaptive cultivation, continuous expansion culture and adaptive cultivation of ore piles are mixed to obtain a concentration of l-8xl0. ⁶ cell/mL mixed bacterial solution, the mixed bacterial liquid is combined according to the cell concentration ratio per unit volume: 30±5.0% of Thiobacillus acidophilus, 15±3.0% of Thiobacillus acidophilus Ferrous oxide Helicobacter pylori 30 soil 5.0%, Thiobacillus thermophilus 12 ± 3.0%, mesophilic sulfur-oxidized sulphide 3 ± 0.5%, metal thiobacillus 2 ± 0.5%, diligent metalococcus 3 ± 0.5%, addiction Acid bacteria 3 ± 0.5%, Phytophthora bacteria 2 ± 0.5%; the acidophilic Thiobacillus ferrooxidans is 16 kinds of deposit number is CCTCC AB 206199, CCTCC AB 206200, CCTCC AB 20620 K CCTCC AB 206202, CCTCC AB One or more of 206203, CCTCC AB 206204, CCTCC AB 206205, CCTCC AB 206206, CCTCC AB 206207, CCTCC AB 206208 CCTCC AB 207053, CCTCC AB 207054, CCTCC AB 207055, CCTCC AB 207056, CCTCC AB 207057, CCTCC AB 207058 Acidophilic sulfur oxide Thiobacillus is one of three types of CCTCC AB206195, CCTCC AB 206196, CCTCC AB 206197; the ferrous oxide of Leptospirillum is 10 kinds of accession number CCTCC AB206158, CCTCC AB 206159, CCTCC AB 206160, CCTCC AB 206161, CCTCC AB 206162, CCTCC AB 206163, CCTCC AB 206164, CCTCC AB 207036 > CCTCC AB 207037, one or several of CCTCC AB 207038; Thiobacillus thermophilum is three types of deposits CCTCC AB207044, CCTCC AB 206175, One or more of CCTCC AB 206176; Thermophilic sulfur-oxidized S. sulphate CCTCC AB207045, Thiophorus ssp. CTCCC AB207047, Dictococcus metaliscoid is one or several of three deposit numbers CCTCC AB207046, CCTCC AB 206191, CCTCC AB 206192 Acidophilus is 14 kinds of deposits as CCTCC AB206219, CCTCC AB 206220 CCTCC AB 20622 K CCTCC AB 206222, CCTCC AB 206223, CCTCC AB 206224, CCTCC AB 206225, CCTCC AB 206226, CCTCC AB 207065, CCTCC AB 207066, CCTCC AB 207067, CCTCC AB 207068, CCTCC AB 207069, CCTCC AB 207070 one or more; Phytophthora CTCCC AB207048.

2. The leaching microorganism combination bacterium according to claim 1, wherein the ore heap adaptive culture is to add -0.074 mm of 2-5% w/v copper ore powder to the chemical medium. Or concentrate as a mixed medium; after the microbial concentration reaches at least l-8x10 ⁷ ceII / mL, and then inoculated into 5-10 tons of ore heap according to l-8x I0 ⁶ ceII / mL, the 矿 line of ore pile adaptive growth, so that after it is in the logarithmic growth phase, the microorganism concentration of at least ^{l-8x l0 6 cdl / mL} , by l-8xl0 ⁶ cell / mL was inoculated into 100-500 tons of ore heap cultured 20-40 days.

3. A method for biometallurgical recovery of copper ore by using the leaching microbial combined bacterial solution according to claim 1 or 2, comprising the steps of: (1) Block ore biolead

Laying the bottom layer and the anti-seepage layer, and pre-cracking the +5-40mm grain-level copper ore large particle lump with a thickness of 200-300mm on the anti-seepage layer as the buffer layer of the yard; continue to be broken. +5-40mm grain size copper ore large particle lump ore is deposited in a thin layer, pre-sprayed with dilute sulfuric acid solution, and then inoculated with the leaching microorganism combination bacteria according to claim 1 or 2 according to l-8x10 ⁶ cell/mL Liquid, start intermittent spray production operation and ventilation, leachate standby;

(2) Powder ore mixing bacteria biological tank dip

Adding the crushed -5mm-grained copper ore fine ore and concentrated sulfuric acid, and the leaching microorganism-containing combined bacterial solution according to claim 1 or 2 to the stirring tank, so that the microbial concentration in the mixed solution is l-8xl0 ⁰ cell/ mL _; stirring and leaching in a stirred tank, the leachate is reserved;

(3) Tailings granulation biopsy

Firstly, the copper ore tailings are pelletized and granulated, the particle size is controlled at 10-20mm, 150-200mm thick copper ore fines with a particle size of 5mm are laid as the bottom layer, and the anti-seepage layer is laid, and the anti-seepage layer is laid flat 200 - 300mm thick grit, as a buffer layer of the yard; then, on the buffer layer, the pelletized copper ore tailings with a particle size of 10-20mm after pelletizing and granulation are laid and piled up. Spraying in advance, and then inoculating the leaching microorganism combined bacterial solution according to claim 1 or 2, the microbial concentration is l-8× ^{10 6} cell/mL, intermittent spraying, and the leaching solution is reserved;

(4) Powder ore and acid block waste rock bioreactor

The copper ore mining acidic massive waste rock with a particle size of 40mm-60mm with a copper content of 0.09-0.3% is laid as the bottom layer, and the thickness is 300-400mm; the anti-seepage layer is covered, and the anti-seepage layer is flat-stacked 200-300mm thick. The copper ore fines with a particle size of 5mm, as a buffer layer of the yard, the multi-layer laying method of the ore heap, first laying the first layer of copper ore acidic massive waste rock, using a mortar pump to pump copper with a mass concentration of 30% The tailings sand pump is pumped onto the waste rock layer, so that the tailings can be evenly and firmly distributed in the ore layer; the second layer of waste rock layer is laid and the tailings sand is pumped; so repeatedly, until the pile height of each layer of the pile is 4- 6M; pre-spraying of sulfuric acid in the early stage of the heap leaching, and then inoculating the leaching microorganism combination solution according to claim 1 or 2, the microbial concentration is l-8× ^{10 6} cell/mL, intermittent spraying, and the leaching solution is reserved;

(5) Pulverized ore and fine grinding copper smelting furnace slag granulation bio-drap

Firstly, the copper smelting furnace slag is crushed and finely ground, and then granulated with the powder ore. The particle size is controlled at 20mm, and the 150-200mm thick powder with a particle size of 5mm is used as the bottom layer, and the upper layer is covered with the anti-seepage layer. The finely ground smelting slag and powder ore of 200-300mm thickness are formed on the top of the infiltration layer as a buffer layer of the yard; then the heap leaching of the finely ground smelting slag and the fine ore by the pelletizing granulation is continued Pre-spraying of sulfuric acid in the early stage of heap leaching, and then inoculating the leaching microorganism combination solution according to claim 1 or 2, the microbial concentration is l-8× ^{10 6} cell/mL, intermittent spraying, and the leaching solution is reserved; (6) extracting one or more of the leachate obtained by the above steps (1) - (5) by electrowinning to prepare electric copper; or using one or more of the leachate obtained by the above steps (1) - (5) Replacement to obtain sponge copper.

The method for biometallurgical recovery of copper ore according to claim 3, wherein in the lump ore biopile immersion according to the step (1), the bottom layer is a coarse sand having a thickness of 300-400 mm. The crushed +5-40mm grain copper ore is thinly piled up, each layer is 5-7m in height, and 4-6 layers are laid; firstly sprayed with a dilute sulfuric acid solution with a pH of 0.9-1.2. The pH of the leachate is maintained at 1.7-1.9, and after the pH of the leachate is stabilized for 48 hours, the leaching microorganism combined bacterial solution according to claim 1 or 2 is inoculated.

The method for biometallurgical recovery of copper ore according to claim 3, wherein in the powder ore mixing bacteria biological tank immersion according to the step (2), the mass concentration of sulfuric acid in the mixed solution in the stirring tank is 30-45g / L; stirring speed is 40-60 rev / min; during the stirring process, air compressor can also be used to pass air to the stirring tank, leaching reaction for 1-3 hours.

The method for biometallurgical recovery of copper ore according to claim 3, wherein in the tailing granulation biological heap leaching described in the step (3), 2% dilute sulfuric acid is added during pelletizing and granulating, The particle size is controlled at 20 mm, and pre-spraying of sulfuric acid is carried out in the early stage of heap leaching to ensure that the pH of the leaching environment is maintained at 1.7-1.9, and the pH value is stable for 24 hours, and the leaching microorganism combination liquid solution according to claim 1 or 2 is inoculated.

The method for biometallurgical recovery of copper ore according to claim 3, wherein in the leaching of the powder ore and the acidic massive waste rock in the step (4), the pre-spraying of the sulfuric acid is carried out in the early stage of the heap leaching. The leaching environment is maintained at a pH of 1.7-1.9, and the pH of the environment is stabilized for 24 hours, and then the inoculum microbial combined bacterial solution according to claim 1 or 2 is inoculated.

The method for biometallurgical recovery of copper ore according to claim 3, wherein the powder ore and the finely ground copper smelting furnace slag granulated biological heap leaching, powder ore and finely ground copper are used in the step (5). When smelting slag granulation, the copper smelting furnace slag is first crushed and finely ground to have a -0.074mm particle size of not less than 50%, and 35-40 g/L of sulfuric acid is used for pelletizing and granulating. After being opened for 8-12 hours, the surface is stabilized and solidified; the pre-spraying of the sulfuric acid is pre-sprayed to ensure that the pH of the leaching environment is maintained at 1.7-1.9, and the environmental pH is stable for 24 hours after claim 1 or 2 The leaching microorganism combined with the bacterial liquid is inoculated.

The method for biometallurgical recovery of copper ore according to claim 3, wherein the anti-seepage layer of the steps (1), (3), (4), (5) is acid-resistant with a thickness of 1 mm to 3 mm. PVC geotextile.