CN102974467A - Beneficiation reagent and of separating and recycling precious metal from cooper anode mud using method thereof - Google Patents

Abstract

The invention belongs to the field of precious metal metallurgy, and in particular relates to a beneficiation agent for separating and recovering precious metals from copper anode slime and a use method thereof. The mineral dressing agent of the present invention, according to the weight ratio, is made up of 1-10 parts by weight of collector pinitol xanthate and pinitol black medicine, 1-10 parts by weight of inhibitor sodium hexametaphosphate and 1-10 parts by weight of foaming agent pinitol oil. 10 parts by weight, the method of separating and recovering precious metals by using mineral dressing agents is as follows: firstly carry out acid leaching pretreatment, then prepare the acid leaching slag into ore pulp, add mineral dressing agents for rough separation, and then conduct twice beneficiation to obtain precious metal ores. The ore dressing agent of the invention has strong selectivity, high separation efficiency for precious metals, high recovery rate of gold and silver, and reduces cost and pollution.

Description

A beneficiation agent for separating and recovering precious metals from copper anode slime and its application method

technical field

The invention belongs to the field of precious metal metallurgy, and in particular relates to a beneficiation agent for separating and recovering precious metals from copper anode slime and a use method thereof. the

Background technique

Copper anode slime is a by-product of copper electrolytic refining and is an important raw material for the recovery of precious metals. In the process of copper electrolysis, the potential of gold, silver and platinum group metals is relatively positive, and it does not electrochemically dissolve on the copper anode and is produced as extremely fine particles. Fall off from the anode to the bottom of the electrolytic cell; elements such as sulfur, selenium and tellurium exist in the form of stable compounds on the anode, and sink to the bottom of the electrolytic cell without electrochemical reaction; insoluble nickel sinks to the bottom of the electrolytic cell in a compound state. There are three representative processes for recovering gold, silver and other precious metals from anode slime at home and abroad: one is the all-wet process, which is "anode slime-pressure leaching copper, tellurium-chloride leaching selenium, gold-alkali leaching lead separation-ammonia immersion silver separation-gold and silver electrolysis"; the second is the (semi) wet process which is based on the wet method and combines the fire method and the wet method, which is currently adopted by most domestic manufacturers. The main process is " Anode slime-sulphating roasting selenium steaming-dilute acid copper separation-chloride gold separation-sodium sodium separation silver-gold and silver electrolysis"; the third is the fire method based on the fire method, and the fire method combined with the wet method and the fire method, the main process It is "anode slime - pressure leaching copper, tellurium - fire smelting, blowing - silver electrolysis - silver anode slime treatment of gold", and its main equipment is Kaldor furnace and pressure leaching kettle. In the existing technology, the following disadvantages generally exist: the dispersion loss of precious metals in each process is very serious; the direct recovery rate of precious metals is low; Many, lead and arsenic and other toxic elements remain seriously; equipment automation is low and energy consumption is high. Using the flotation process to treat copper anode slime can greatly improve the processing capacity of copper anode slime, create favorable conditions for smelting, and reduce flux consumption. However, this method is still rarely used in China to treat copper anode slime. Related experimental studies Insufficient, especially the immature research on beneficiation agents and beneficiation methods for anode slime, resulting in unsatisfactory beneficiation and smelting effects and high content of precious metals in tailings. the

Contents of the invention

Aiming at the problems existing in the separation and recovery technology of precious metals in copper anode slime, the present invention provides a kind of mineral processing agent for separating and recovering precious metals from copper anode slime and its use method. Collectors, combined with appropriate separation and smelting processes, efficiently separate precious metals from anode slime. the

A beneficiation agent for separating and recovering precious metals from copper anode slime, comprising 1 to 10 parts by weight of a collector, 1 to 10 parts by weight of an inhibitor, and 1 to 10 parts by weight of a foaming agent according to the weight ratio, wherein the The collectors are pinitol xanthate and pinitol black medicine, the molar ratio of pinitol xanthate and pinitol black medicine is 1: (0.01~25), the inhibitor is sodium hexametaphosphate, and the foaming agent is pinitol Oil. the

，其制备方法是：按摩尔比松醇油：氢氧化钠：二硫化碳=1:1:1.2配料，在15～40℃下反应1～3h，得到松醇黄药。  The pinitol xanthate is

, the preparation method is: massaging pinitol oil: sodium hydroxide: carbon disulfide = 1:1:1.2 ingredients, reacting at 15-40°C for 1-3 hours to obtain pinitol xanthate.

the

，其制备方法是：按照摩尔比松醇油：五硫化二磷：氢氧化钠=4:1:2配料，在20～80℃下反应1～3h，得到松醇黑药。 Described pinitol black medicine is

, and its preparation method is: according to the molar ratio of pinitol oil: phosphorus pentasulfide: sodium hydroxide = 4:1:2 ingredients, react at 20-80 DEG C for 1-3 hours, to obtain pinitol black medicine.

The method for separating and recovering precious metals from copper anode slime by using the above-mentioned dressing agent is carried out according to the following steps:

(1) Pretreatment: Pretreatment: Mix copper anode slime and sulfuric acid at a weight ratio of 1:(0.1~5), roast at 450~850°C for 1~3h, and mix the obtained slag and sulfuric acid at a weight ratio of 1:(0.1 ~5) Mixing, acid leaching at 20-90°C for 1-3 hours, the acid leaching residue obtained is washed and then dried; the sulfuric acid concentration is 50-450g/L;

(2) Flotation: add water to the dried acid leaching residue to prepare pulp with a weight concentration of 5% to 45%, adjust the pH of the pulp to 0.5 to 13.5, and add mineral processing agents to the pulp: collector pinitol xanthate Hepine alcohol black medicine 1~10kg/t, inhibitor sodium hexametaphosphate 1~10kg/t, foaming agent pine alcohol oil 1~10kg/t for rough separation to obtain rough concentrate and rough tailings;

Add water to the coarse concentrate to prepare pulp with a mass concentration of 15-35%, adjust the pH of the pulp to 0.5-7.5, add collectors pinitol xanthate and pinitol black medicine 1-3kg/t to the pulp for one-time beneficiation , obtain one-time concentrated ore and one-time refined tailings, repeat the above process for one-time concentrated ore, and obtain second-time concentrated ore and secondary-selected tailings, and the second-time concentrated ore is precious metal concentrate;

Add water to the thick tailings to make a pulp with a weight concentration of 15-35%, adjust the pH of the pulp to 2.5-12.5, add collectors pinitol xanthate and pinitol black medicine 1-4kg/t, and obtain scavenging concentrate and tailings;

The sweeping concentrate and the above-mentioned first-time beneficiation tailings return to the roughing step for roughing again;

The secondary beneficiation tailings return to the first beneficiation step for another beneficiation.

The molar ratio of the collector pinitol xanthate to pinitol black medicine is 1: (0.01-25). the

Compared with prior art, feature and beneficial effect of the present invention are:

The collector in the past ore dressing agent is simple xanthate or black medicine, and the mineral dressing agent of the present invention is self-made pinitol xanthate and pinitol black medicine, because the hydrophobicity of pinitol xanthate and pinitol black medicine The carbon chain is long, and the chain contains a ring structure, which has a large steric hindrance. In the flotation process, the micelles formed between the collector and the mineral are related to the length and structure of the hydrocarbon chain. The lower the concentration of the collector, the greater the steric hindrance, and the more limited the types of minerals suitable for collector collection. Therefore, the selectivity of pinitol black medicine and pinitol black medicine is strong, the separation efficiency of precious metals is high, and the recovery of gold and silver High rate.

Using the mineral dressing agent of the present invention combined with the dressing and smelting process can save the expensive lead furnace in the traditional process, improve productivity, reduce costs, and a large amount of base metal impurities enter the tailings, reducing lead pollution and smoke pollution, It improves the working conditions and has high promotional value. the

Description of drawings

Accompanying drawing 1 is the process flow diagram of the method for separating and recovering precious metals from copper anode slime according to the present invention. the

Detailed ways

The present invention is described in further detail below in conjunction with embodiment. The copper anode slime used in the present invention is the copper anode slime of a traditional smelter, and the weight contents of the main valuable metals copper, lead, silver and gold are 16.35%, 13.74%, 9.94% and 0.21% respectively. the

Example 1

An ore dressing agent for separating and recovering precious metals from copper anode slime, comprising 3 parts by weight of a collector, 10 parts by weight of an inhibitor and 10 parts by weight of a foaming agent, wherein the collector is pinitol Xanthate and pinitol black medicine, the molar ratio of pinitol xanthate and pinitol black medicine is 2:1, the inhibitor is sodium hexametaphosphate, and the foaming agent is pinitol oil.

The preparation method of the pinitol xanthate is as follows: massaging pinitol oil: sodium hydroxide: carbon disulfide=1:1:1.2, reacting at 15° C. for 3 hours to obtain pinitol xanthate. the

The preparation method of the pinitol black medicine is as follows: according to the molar ratio of pinitol oil: phosphorus pentasulfide: sodium hydroxide = 4:1:2, react at 80° C. for 1 hour to obtain the pinitol black medicine. the

The method for separating and recovering precious metals from copper anode slime by using the above-mentioned dressing agent is carried out according to the following steps:

(1) Pretreatment: Mix copper anode slime and sulfuric acid at a weight ratio of 1:1, roast at 450°C for 3 hours, mix the obtained slag with sulfuric acid at a weight ratio of 1:1, and pickle at 20°C for 3 hours to obtain Acid leaching residue is dried after washing; the concentration of sulfuric acid is 50g/L;

(2) Flotation: add water to the dried acid leaching residue to prepare a pulp with a weight concentration of 45%, adjust the pH of the pulp to 0.5, and add mineral dressing agents to the pulp: collector pinitol xanthate and pinitol black medicine 3kg/t, inhibitor sodium hexametaphosphate 10kg/t, foaming agent pinitol oil 10kg/t for roughing to obtain rough concentrate and rough tailings;

Add water to the coarse concentrate to prepare pulp with a mass concentration of 35%, adjust the pH of the pulp to 0.5, add collectors pinitol xanthate and pinitol black medicine 1kg/t to the pulp for a beneficiation, and obtain a beneficiation concentrate Ores and primary concentrate tailings, repeat the above process for primary concentrate concentrates to obtain secondary concentrate concentrates and secondary concentrate tailings, the secondary concentrate concentrates are precious metal concentrates;

Add water to the thick tailings to prepare a slurry with a weight concentration of 35%, adjust the pH of the slurry to 2.5, add collectors pinitol xanthate and pinitol black medicine 1kg/t for scavenging, and obtain scavenging concentrates and tailings;

The sweeping concentrate and the above-mentioned first-time beneficiation tailings return to the roughing step for roughing again;

The secondary beneficiation tailings return to the first beneficiation step for another beneficiation.

The molar ratio of the collector pinitol xanthate to pinitol black medicine is 2:1. the

Comparative example 1

(1) Mineral dressing agent for anode slime collector: anode slime dressing agent is a combined formula that uses commercially available xanthate and commercially available black medicine as collector, sodium hexametaphosphate as inhibitor, and terpineol oil as foaming agent , The molar ratio of collector xanthate and black drug is 2:1.

(2) Mineral processing method for separating and recovering precious metals from anode slime: the same as in Example 1, except that the collectors of mineral processing agents are commercially available xanthate and black medicine. the

The results of the analysis of the concentrate and tailings are shown in Table 1. the

As can be seen from Table 1, the ore dressing agent and the process flow of the anode slime provided by the present invention can realize the effect of efficient separation and recovery of precious metals, the recovery rate of gold can reach more than 95%, the recovery rate of silver can reach more than 94%, and the anode slime The lead content in precious metals is reduced to less than 15%. And compared with the commercial medicines, the self-made medicines showed obvious superiority in every index. the

Example 2

An ore dressing agent for separating and recovering precious metals from copper anode slime, comprising 10 parts by weight of a collector, 1 part by weight of an inhibitor and 1 part by weight of a foaming agent according to the weight ratio, wherein the collector is pinitol Xanthate and pinitol black medicine, the molar ratio of pinitol xanthate and pinitol black medicine is 100:1, the inhibitor is sodium hexametaphosphate, and the foaming agent is pinitol oil.

The preparation method of the pinitol xanthate is as follows: massaging pinitol oil: sodium hydroxide: carbon disulfide=1:1:1.2, reacting at 40° C. for 1 hour to obtain pinitol xanthate. the

The preparation method of the pinitol black medicine is as follows: according to the molar ratio of pinitol oil: phosphorus pentasulfide: sodium hydroxide = 4:1:2, react at 20° C. for 3 hours to obtain the pinitol black medicine. the

The method for separating and recovering precious metals from copper anode slime by using the above-mentioned dressing agent is carried out according to the following steps:

(1) Pretreatment: Roast copper anode slime and sulfuric acid at 850°C for 1 hour, mix the obtained slag and sulfuric acid at a weight ratio of 1:5, pickle at 90°C for 1 hour, and then wash and bake the obtained acid leaching residue dry; the concentration of sulfuric acid is 450g/L;

(2) Flotation: add water to the dried acid leaching slag to prepare a pulp with a weight concentration of 20%, adjust the pH of the pulp to 13.5, and add mineral dressing agents to the pulp: collector pinitol xanthate and pinitol black medicine 10kg/t, inhibitor sodium hexametaphosphate 1kg/t, foaming agent pinitol oil 1kg/t for roughing to obtain rough concentrate and rough tailings;

Add water to the coarse concentrate to make a pulp with a mass concentration of 20%, adjust the pH of the pulp to 7.5, add collectors pinitol xanthate and pinitol black medicine 3kg/t to the pulp for a beneficiation, and obtain a beneficiation concentrate Ores and primary concentrate tailings, repeat the above process for primary concentrate concentrates to obtain secondary concentrate concentrates and secondary concentrate tailings, the secondary concentrate concentrates are precious metal concentrates;

Add water to the thick tailings to prepare a pulp with a weight concentration of 15%, adjust the pH of the pulp to 12.5, add collectors pinitol xanthate and pinitol black medicine 4kg/t, and obtain scavenging concentrate and tailings;

The sweeping concentrate and the above-mentioned first-time beneficiation tailings return to the roughing step for roughing again;

The secondary beneficiation tailings return to the first beneficiation step for another beneficiation.

The molar ratio of the collector pinitol xanthate to pinitol black medicine is 20:1. the

Comparative example 2

(1) Mineral dressing agent for anode slime collector: anode slime dressing agent is a combined formula that uses commercially available xanthate as collector, sodium hexametaphosphate as inhibitor, and terpineol oil as foaming agent.

(2) The beneficiation method for separating and recovering precious metals from anode slime is the same as in Example 2, except that the collector in the beneficiation agent is commercially available xanthate. the

The results of the analysis of the concentrate and tailings are shown in Table 1. the

As can be seen from Table 1, the ore dressing agent and the process flow of the anode slime provided by the present invention can realize the effect of efficient separation and recovery of precious metals, the recovery rate of gold can reach more than 95%, the recovery rate of silver can reach more than 94%, and the anode slime The lead content in precious metals is reduced to less than 15%. And compared with the commercial medicines, the self-made medicines showed obvious superiority in every index. the

Example 3

A beneficiation agent for separating and recovering precious metals from copper anode slime, comprising 1 part by weight of collector, 5 parts by weight of inhibitor and 5 parts by weight of foaming agent according to the weight ratio, wherein the collector is pinitol Xanthate and pinitol black medicine, the molar ratio of pinitol xanthate and pinitol black medicine is 1:25, the inhibitor is sodium hexametaphosphate, and the foaming agent is pinitol oil.

The preparation method of the pinitol xanthate is as follows: massaging pinitol xanthate oil: sodium hydroxide: carbon disulfide=1:1:1.2, reacting at 30°C for 1.5h to obtain pinitol xanthate. the

The preparation method of the pinitol black drug is as follows: according to the molar ratio of pinitol oil: phosphorus pentasulfide: sodium hydroxide = 4:1:2, react at 60° C. for 2 hours to obtain the pinitol black drug. the

The method for separating and recovering precious metals from copper anode slime by using the above-mentioned dressing agent is carried out according to the following steps:

(1) Pretreatment: Mix copper anode slime and sulfuric acid at a weight ratio of 10:1, roast at 650°C for 2 hours, mix the obtained slag with sulfuric acid at a weight ratio of 10:1, and pickle at 60°C for 2 hours to obtain The acid leaching residue is dried after washing; the concentration of sulfuric acid is 250g/L;

(2) Flotation: add water to the dried acid leaching residue to prepare a pulp with a weight concentration of 30%, adjust the pH of the pulp to 2, and add mineral dressing agents to the pulp: collector pinitol xanthate and pinitol black medicine 1kg/t, inhibitor sodium hexametaphosphate 5kg/t, foaming agent terpineol oil 5kg/t for roughing to obtain rough concentrate and rough tailings;

Add water to the coarse concentrate to make a pulp with a mass concentration of 5%, adjust the pH of the pulp to 13.5, add collectors pinitol xanthate and pinitol black medicine 2kg/t to the pulp for a beneficiation, and obtain a beneficiation concentrate Ores and primary concentrate tailings, repeat the above process for primary concentrate concentrates to obtain secondary concentrate concentrates and secondary concentrate tailings, the secondary concentrate concentrates are precious metal concentrates;

Add water to the thick tailings to prepare a pulp with a weight concentration of 20%, adjust the pH of the pulp to 5, add collectors pinitol xanthate and pinitol black medicine 3kg/t, and obtain scavenging concentrate and tailings;

The sweeping concentrate and the above-mentioned first-time beneficiation tailings return to the roughing step for roughing again;

The secondary beneficiation tailings return to the first beneficiation step for another beneficiation.

The molar ratio of the collector pinitol xanthate and pinitol black medicine is 1:25. the

Comparative example 3

(1) Mineral dressing agent for anode slime collector: anode slime dressing agent is a combination formula of commercial black medicine as collector, sodium hexametaphosphate as inhibitor, and terpineol oil as foaming agent.

(2) The beneficiation method for separating and recovering precious metals from anode slime: the same as in Example 3. the

The results of the analysis of the concentrate and tailings are shown in Table 1. the

As can be seen from Table 1, the ore dressing agent and the process flow of the anode slime provided by the present invention can realize the effect of efficient separation and recovery of precious metals, the recovery rate of gold can reach more than 95%, the recovery rate of silver can reach more than 94%, and the anode slime The lead content in precious metals is reduced to less than 15%. And compared with the commercial medicines, the self-made medicines showed obvious superiority in every index. the

the

Table 1 Adopting the mineral dressing agent of the present invention to separate precious metals from copper anode slime and the influence of existing agents on the mineral processing effect of anode slime

Claims (5)

1. one kind is separated the beneficiation reagent that reclaims noble metal from copper anode mud, it is characterized in that according to weight proportion, formed by collecting agent 1 ~ 10 weight portion, inhibitor 1 ~ 10 weight portion and foaming agent 1 ~ 10 weight portion, wherein said collecting agent is pine camphor xanthate and pine camphor black powder, the mol ratio of pine camphor xanthate and pine camphor black powder is 1:(0.01 ~ 25), inhibitor is calgon, and foaming agent is terpenic oil.

2. a kind of beneficiation reagent that reclaims noble metal that separates from copper anode mud according to claim 1 is characterized in that described pine camphor xanthate is

, its preparation method is: terpenic oil in molar ratio: NaOH: carbon disulfide=1:1:1.2 batching at 15～40 ℃ of lower reaction 1～3h, obtains the pine camphor xanthate.

3. a kind of beneficiation reagent that reclaims noble metal that separates from copper anode mud according to claim 1 is characterized in that described pine camphor black powder is

, its preparation method is: according to the mol ratio terpenic oil: phosphorus pentasulfide: NaOH=4:1:2 batching at 20～80 ℃ of lower reaction 1～3h, obtains the pine camphor black powder.

4. use beneficiation reagent as claimed in claim 1 from copper anode mud, to separate the method that reclaims noble metal, it is characterized in that carrying out according to following steps:

(1) preliminary treatment: with copper anode mud and sulfuric acid according to weight ratio 1:(0.1 ~ 5) mix, in 450～850 ℃ of roasting 1～3h, gained is roasted slag and sulfuric acid according to weight ratio 1:(0.1 ~ 5) mix, in 20～90 ℃ of leaching time 1～3h, the acid leaching residue that obtains is through the washing post-drying; Described sulfuric acid concentration is 50～450g/L;

(2) flotation: the acid leaching residue after will drying adds water, and to be mixed with weight concentration be 5%～45% ore pulp, regulating pH values of pulp is 0.5～13.5, add beneficiation reagent in the ore pulp: collecting agent 1～10kg/t, inhibitor calgon 1～10kg/t, foaming agent terpenic oil 1～10kg/t roughly selects, and obtains rough concentrate and thick mine tailing;

Rough concentrate is added water, and to be mixed with mass concentration be 15～35% ore pulp, regulating pH values of pulp is 0.5～7.5, add collecting agent 1～3kg/t in the ore pulp and carry out primary cleaning, obtain primary cleaning concentrate and primary cleaner tailing, the primary cleaning concentrate is repeated said process, obtain recleaning concentrate and recleaning mine tailing, the recleaning concentrate is the noble metal concentrate;

Thick mine tailing is added water, and to be mixed with weight concentration be 15～35% ore pulp, and regulating pH values of pulp is 2.5～12.5, adds collecting agent 1～4kg/t, obtains scavenger concentrate and mine tailing;

Described scavenger concentrate and above-mentioned primary cleaner tailing return to be roughly selected step and again roughly selects;

Described recleaning mine tailing returns the primary cleaning step and again carries out primary cleaning.

5. the method that from copper anode mud, separate to reclaim noble metal according to claim 4, the mol ratio that it is characterized in that described collecting agent pine camphor xanthate and pine camphor black powder is 1:(0.01 ~ 25).

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