阅读说明：本技术 一种复杂多金属硫化矿铜铅锌砷浮选分离方法 (Flotation separation method for copper, lead, zinc and arsenic in complex multi-metal sulfide ore ) 是由 齐向红 危刚 唐平宇 田江涛 张凯熙 葛阳阳 于 2020-06-04 设计创作，主要内容包括：本发明涉及冶金技术领域,且公开了一种复杂多金属硫化矿铜铅锌砷浮选分离方法,包括以下步骤：步骤S1：磨矿作业：将原矿破碎并将其与水投入到球磨机内进行磨矿,球磨机的排料条件为磨矿细度达到-0.074mm占65～70％；步骤S2：铜铅锌砷混合浮选作业：在浮选机内加入稀硫酸调节矿浆pH值为至弱碱性,以丁基黄药作为捕收剂、松醇油作为起泡剂,并在添加过程中分别搅拌后进行一次粗选、三次精选及两次扫选,得到铜铅锌砷混合精矿及尾矿。本发明设计所使用到药剂为常规选矿药剂,对环境无污染、价格低廉、市场易于购得,方便成本控制,铜铅锌砷有价元素分选效果好,获得精矿产品品质高,精矿产品中金属互含率低。(The invention relates to the technical field of metallurgy, and discloses a copper, lead, zinc and arsenic flotation separation method for complex multi-metal sulfide ores, which comprises the following steps: step S1: ore grinding operation: crushing raw ore and putting the crushed raw ore and water into a ball mill for grinding, wherein the discharge condition of the ball mill is that the grinding fineness of the ball mill reaches-0.074 mm and accounts for 65-70%; step S2: copper-lead-zinc-arsenic mixed flotation operation: adding dilute sulfuric acid into a flotation machine to adjust the pH value of the ore pulp to be alkalescent, taking butyl xanthate as a collecting agent and terpineol oil as a foaming agent, stirring respectively in the adding process, and then carrying out primary roughing, tertiary fine concentration and twice scavenging to obtain copper-lead-zinc-arsenic mixed concentrate and tailings. The reagent used in the design of the invention is a conventional beneficiation reagent, has no pollution to the environment, low price, easy acquisition in the market, convenient cost control, good separation effect of copper, lead, zinc and arsenic valuable elements, high quality of the obtained concentrate product and low metal content in the concentrate product.)

1. A flotation separation method for copper, lead, zinc and arsenic in complex multi-metal sulfide ores is characterized by comprising the following steps:

step S1: ore grinding operation: crushing raw ore, putting the crushed raw ore and water into a ball mill for grinding, wherein the ratio of the raw ore to the water is 1: 1, discharging the material by a ball mill under the condition that the grinding fineness reaches-0.074 mm and accounts for 65-70%;

step S2: copper-lead-zinc-arsenic mixed flotation operation: adding dilute sulfuric acid into a flotation machine to adjust the pH value of the ore pulp to be alkalescent, taking butyl xanthate as a collecting agent and pinitol oil as a foaming agent, stirring respectively in the adding process, and then carrying out primary roughing, tertiary fine selection and twice scavenging to obtain copper-lead-zinc-arsenic mixed concentrate and tailings;

step S3: separating copper, lead and zinc from arsenic: adding sodium sulfide and activated carbon into the copper-lead-zinc-arsenic bulk concentrate obtained in the step S2 for drug removal treatment, and then sequentially adding a combined inhibitor for separation of copper, lead, zinc and arsenic to obtain the copper-lead-zinc bulk concentrate and arsenic concentrate, wherein the ingredients of the combined inhibitor are lime, sodium humate, bleaching powder, butyl xanthate and pine oil;

step S4: copper and lead-zinc separation I: adding 500-700 g/t of sodium sulfide into the copper-lead-zinc bulk concentrate in the copper-lead-zinc bulk concentrate obtained in the step S3, stirring for 6 minutes for secondary reagent removal, sequentially adding a combined inhibitor with the components of 2000-3000 g/t of zinc sulfate, 1500-2500 g/t of sodium sulfite and 100-150 g/t of sodium carboxymethylcellulose, sequentially adding 15-25 g/t of Z-200# and 10-20 g/t of pine oil, stirring for 5 minutes, 3 minutes and 1 minute respectively, then separating copper from lead and zinc, feeding the concentrate obtained in the first step of separating copper from lead and zinc into a second step of separating copper from lead and zinc, and feeding tailings into a copper scavenging operation;

step S5: and (3) separating copper from lead and zinc II: sequentially adding a combined inhibitor with the components of 1000-1500 g/t zinc sulfate, 800-1500 g/t sodium sulfite and 50-100 g/t sodium carboxymethylcellulose into a flotation machine, sequentially adding 15-25 g/t Z-200# and 10-20 g/t pine oil, stirring for 5 minutes, 3 minutes and 1 minute respectively, and then carrying out copper-lead-zinc separation II, wherein the concentrate obtained by the copper-lead-zinc separation II is a final copper concentrate, and the middling of the copper-lead-zinc separation II returns to the copper-lead-zinc separation I;

step S6: copper scavenging: and (3) sequentially adding 10-20 g/t of Z-200# and 5-15 g/t of pinitol oil into the flotation machine, stirring for 3 minutes and 1 minute respectively, then carrying out copper scavenging, returning copper from scavenged middlings to separate I from lead and zinc, and scavenging tailings to obtain final lead and zinc bulk concentrates.

2. The flotation separation method for copper, lead, zinc and arsenic in complex polymetallic sulfide ores according to claim 1, wherein in step S2, dilute sulfuric acid is added into a flotation machine to adjust the pH value of ore pulp to 5-6, butyl xanthate 70-90 g/t and terpineol 25-30 g/t are added, the mixture is stirred for 2 minutes and 1 minute respectively, then copper, lead, zinc and arsenic mixed flotation roughing is carried out, the obtained copper, lead, zinc and arsenic mixed rough concentrate enters a concentration operation, and rougher tailings enter a scavenging operation.

3. The method for separating copper, lead, zinc and arsenic from complex polymetallic sulphide ores according to claim 1, wherein in step S2, the copper, lead, zinc and arsenic concentration I is performed after adding 300-400 g/t of water glass into a flotation machine and stirring for 2 minutes, the concentrate of the copper, lead, zinc and arsenic concentration I enters the copper, lead, zinc and arsenic concentration II, and the middlings of the copper, lead, zinc and arsenic concentration I are returned to the copper, lead, arsenic roughing operation.

4. The method for separating copper, lead, zinc and arsenic from complex polymetallic sulfide ores according to claim 1, wherein in step S2, the copper, lead, zinc and arsenic concentration II is performed after adding 150-200 g/t of water glass into a flotation machine and stirring for 2 minutes, the copper, lead, zinc and arsenic concentration II concentrate enters the copper, lead, zinc and arsenic concentration III, and the copper, lead, zinc and arsenic concentration II middlings return to the copper, lead, zinc and arsenic mixed rough concentrate concentration I.

5. The method for separating copper, lead, zinc and arsenic from complex polymetallic sulfide ores according to claim 1, wherein in step S2, the copper, lead, zinc and arsenic concentration III is performed after the water glass is added in the flotation machine at a dosage of 50-100 g/t and stirred for 2 minutes, the copper, lead, zinc and arsenic concentration III concentrate is finally a copper, lead, zinc and arsenic bulk concentrate, and the middlings in the copper, lead, zinc and arsenic concentration III are returned to the copper, lead, arsenic bulk concentrate concentration II.

6. The method for flotation separation of copper, lead and zinc as in claim 1, wherein in step S2, butyl xanthate 30-40 g/t and terpineol 10-15 g/t are added into a flotation machine, and after stirring for 2 minutes and 1 minute respectively, copper, lead and zinc as scavenging is performed for first time, tailings of copper, lead and zinc as scavenging are fed into a copper, lead and zinc as scavenging for second time, and middlings of copper, lead and zinc as scavenging for first time are returned to the copper, lead and zinc as roughing operation.

7. The method for flotation separation of copper, lead and zinc as in claim 1, wherein in step S2, butyl xanthate 15-20 g/t and terpineol 5-10 g/t are added into a flotation machine, and after stirring for 2 minutes and 1 minute respectively, copper, lead and zinc as scavenging ii is performed, wherein tailings of the copper, lead and zinc as scavenging ii are final tailings, and middlings of the copper, lead and zinc as scavenging ii are returned to the copper, lead and zinc as scavenging i.

8. The method for flotation separation of copper, lead and zinc as in claim 1, wherein in step S3, 500-600 g/t of sodium sulfide and 700-800 g/t of activated carbon are added into the copper, lead, zinc and arsenic bulk concentrate simultaneously, after stirring for 8 minutes to achieve a drug removal effect, a combined inhibitor containing 800-1000 g/t of lime, 200-300 g/t of sodium humate and 600-800 g/t of bleaching powder is sequentially added, 40-60 g/t of butyl xanthate and 10-20 g/t of terpineol oil are sequentially added, and after stirring for 4 minutes, 2 minutes and 1 minute respectively, copper, lead and zinc are separated from arsenic, the concentrate obtained by separating copper, lead and arsenic is copper, lead and zinc bulk concentrate, and tailings enter copper, lead and zinc scavenging.

9. The method for flotation separation of copper, lead, zinc and arsenic in the complex polymetallic sulphide ore according to claim 1, wherein in step S3, a combined inhibitor comprising 400-600 g/t of lime, 100-200 g/t of sodium humate and 300-500 g/t of bleaching powder is sequentially added into a flotation machine, 20-30 g/t of butyl xanthate and 5-10 g/t of pine oil are sequentially added, the mixture is stirred for 4 minutes, 2 minutes and 1 minute respectively, copper, lead and zinc scavenging is performed, scavenged middlings are returned to the copper, lead and zinc and arsenic separation operation, and tailings are final arsenic concentrates.

Technical Field

The invention relates to the technical field of metallurgy, in particular to a copper-lead-zinc-arsenic flotation separation method for complex multi-metal sulfide ores.

Background

Non-ferrous metal mineral resources play an important role in national economy and are widely applied to various industries and fields. The polymetallic sulphide ore is the largest mineral resource for extracting nonferrous metals, high-grade high-quality resources are exhausted due to continuous development in recent years, the types of copper, lead and zinc resources are complex, the content of useful minerals is relatively low, the embedding relationship among the minerals is complex and changeable, and the polymetallic copper, lead and zinc ore becomes a difficult problem in the beneficiation of the polymetallic sulphide ore. In addition, the multi-metal sulfide ore is often associated with arsenic-containing minerals, arsenic is a toxic mineral product and has great pollution and harm to the environment and organisms, the arsenic minerals are often mixed into copper, lead and zinc concentrate in the ore dressing process, and toxic and harmful substances are generated in the subsequent smelting and acid making processes to seriously pollute the environment and influence the ecological balance, so that the research on separating arsenic from the multi-metal sulfide ore containing arsenic has very important significance in the aspects of environmental protection and improvement of dressing and smelting benefits.

The beneficiation of copper-lead-zinc polymetallic sulphide ores at home and abroad is mainly carried out by flotation, and the traditional process is a preferential flotation process and a partial mixing preferential flotation process. A preferential flotation process: according to the sequence of floatability and floating speed among sulfide minerals such as copper, lead, zinc and the like in the ore, copper concentrate, lead concentrate, zinc concentrate and tailings are respectively obtained by flotation from the ore pulp in sequence. The method is suitable for ores with simple mineral composition, high raw ore grade, large difference of floatability among useful ores and coarse embedded granularity. Partial mixing preferential flotation process: two kinds of useful minerals with similar floatability are selected into the bulk concentrate, and then separation flotation is carried out, namely copper sulfide and lead ores with similar floatability are selected into bulk concentrate, then copper and lead separation is carried out, and the copper and lead tailings are reactivated to select zinc concentrate. Is suitable for ores with similar floatability, and is the most widely applied process at present.

The prior flotation process and the partial mixing prior flotation process both use a thio-compound as a collector to float nonferrous metal sulfides, arsenic-containing minerals are usually floated into concentrate in the flotation process, the quality of the concentrate is influenced, and simultaneously, the loss and the waste of arsenic resources are caused. The method is characterized in that a part of mixed preferential flotation process is adopted for multi-metal sulfide ores with close mineral symbiotic relationship and fine embedded particle size to obtain copper-lead bulk concentrates, the most effective method for separating copper from lead at present is to use cyanide to inhibit lead flotation and potassium dichromate to inhibit lead flotation, and the defects are that cyanide is extremely toxic and heavy chromate ions can cause serious pollution to the environment. Based on the analysis, aiming at the problem of the separation of copper, lead, zinc and arsenic in the multi-metal sulfide ore, the development of a mineral separation process which has the advantages of good separation effect, simple flow and environmental-friendly medicament system has important practical significance, so that a complex flotation separation method for the copper, lead, zinc and arsenic in the multi-metal sulfide ore is provided.

Disclosure of Invention

The invention aims to solve the defects of the prior art, and provides the flotation separation method for the copper, lead, zinc and arsenic in the complex multi-metal sulfide ore, which is environment-friendly, low in production cost and good in separation effect.

In order to achieve the purpose, the invention adopts the following technical scheme:

a copper, lead, zinc and arsenic flotation separation method for complex multi-metal sulfide ores comprises the following steps:

step S1: ore grinding operation: crushing raw ore, putting the crushed raw ore and water into a ball mill for grinding, wherein the ratio of the raw ore to the water is 1: 1, discharging the material by a ball mill under the condition that the grinding fineness reaches-0.074 mm and accounts for 65-70%;

step S2: copper-lead-zinc-arsenic mixed flotation operation: adding dilute sulfuric acid into a flotation machine to adjust the pH value of the ore pulp to be alkalescent, taking butyl xanthate as a collecting agent and terpineol oil as a foaming agent, stirring respectively in the adding process, and then carrying out primary roughing, tertiary fine concentration and twice scavenging to obtain copper-lead-zinc-arsenic mixed concentrate and tailings;

step S3: separating copper, lead and zinc from arsenic: adding sodium sulfide and activated carbon into the copper-lead-zinc-arsenic bulk concentrate obtained in the step S2 for drug removal treatment, and then sequentially adding a combined inhibitor for separation of copper, lead, zinc and arsenic to obtain the copper-lead-zinc bulk concentrate and arsenic concentrate, wherein the ingredients of the combined inhibitor are lime, sodium humate, bleaching powder, butyl xanthate and pine oil;

step S4: copper and lead-zinc separation I: adding 500-700 g/t of sodium sulfide into the copper-lead-zinc bulk concentrate in the copper-lead-zinc bulk concentrate obtained in the step S3, stirring for 6 minutes for secondary reagent removal, sequentially adding a combined inhibitor with the components of 2000-3000 g/t of zinc sulfate, 1500-2500 g/t of sodium sulfite and 100-150 g/t of sodium carboxymethylcellulose, sequentially adding 15-25 g/t of Z-200# and 10-20 g/t of pine oil, stirring for 5 minutes, 3 minutes and 1 minute respectively, then separating copper from lead and zinc, feeding the concentrate obtained in the first step of separating copper from lead and zinc into a second step of separating copper from lead and zinc, and feeding tailings into a copper scavenging operation;

step S5: and (3) separating copper from lead and zinc II: sequentially adding a combined inhibitor with the components of 1000-1500 g/t zinc sulfate, 800-1500 g/t sodium sulfite and 50-100 g/t sodium carboxymethylcellulose into a flotation machine, sequentially adding 15-25 g/t Z-200# and 10-20 g/t pine oil, stirring for 5 minutes, 3 minutes and 1 minute respectively, and then carrying out copper-lead-zinc separation II, wherein the concentrate obtained by the copper-lead-zinc separation II is a final copper concentrate, and the middling of the copper-lead-zinc separation II returns to the copper-lead-zinc separation I;

step S6: copper scavenging: and (3) sequentially adding 10-20 g/t of Z-200# and 5-15 g/t of pinitol oil into the flotation machine, stirring for 3 minutes and 1 minute respectively, then carrying out copper scavenging, returning copper from scavenged middlings to separate I from lead and zinc, and scavenging tailings to obtain final lead and zinc bulk concentrates.

Preferably, in the step S2, dilute sulfuric acid is added into the flotation machine to adjust the pH value of the ore pulp to 5-6, butyl xanthate 70-90 g/t and terpineol 25-30 g/t are added, the mixture is stirred for 2 minutes and 1 minute respectively, then copper-lead-zinc-arsenic mixed flotation roughing is performed, the obtained copper-lead-zinc-arsenic mixed rough concentrate enters a concentration operation, and rougher tailings enter a scavenging operation.

Preferably, in the step S2, the amount of the added water glass in the flotation machine is 300-400 g/t, the mixture is stirred for 2 minutes, then copper-lead-zinc-arsenic concentration i is performed, the concentrate of the copper-lead-zinc-arsenic concentration i enters copper-lead-zinc-arsenic concentration ii, and the middlings of the copper-lead-zinc-arsenic concentration i are returned to the copper-lead-zinc-arsenic roughing operation.

Preferably, in the step S2, the copper-lead-zinc-arsenic concentration II is performed after the adding of 150-200 g/t of water glass in the flotation machine and stirring for 2 minutes, the copper-lead-zinc-arsenic concentration II concentrate enters the copper-lead-zinc-arsenic concentration III, and the middlings in the copper-lead-zinc-arsenic concentration II are returned to the copper-lead-zinc-arsenic mixed rough concentrate concentration I.

Preferably, in the step S2, the copper-lead-zinc-arsenic concentration iii is performed after the addition of water glass in an amount of 50 to 100g/t in the flotation machine and stirring for 2 minutes, the concentrate of the copper-lead-zinc-arsenic concentration iii is finally a copper-lead-zinc-arsenic bulk concentrate, and the middlings of the copper-lead-zinc-arsenic concentration iii are returned to the copper-lead-zinc-arsenic bulk concentrate concentration ii.

Preferably, in the step S2, 30-40 g/t of butyl xanthate and 10-15 g/t of terpineol oil are added into the flotation machine, the mixture is stirred for 2 minutes and 1 minute respectively, copper-lead-zinc-arsenic scavenging I is performed, tailings of the copper-lead-zinc-arsenic scavenging I enter a copper-lead-zinc-arsenic scavenging II, and middlings of the copper-lead-zinc-arsenic scavenging I are returned to the copper-lead-zinc-arsenic roughing operation.

Preferably, in the step S2, adding 15-20 g/t of butyl xanthate and 5-10 g/t of terpineol oil into the flotation machine, stirring for 2 minutes and 1 minute respectively, and then performing copper-lead-zinc-arsenic scavenging ii, wherein the tailings of the copper-lead-zinc-arsenic scavenging ii are final tailings, and the middlings of the copper-lead-zinc-arsenic scavenging ii are returned to the copper-lead-zinc-arsenic scavenging i.

Preferably, in the step S3, 500-600 g/t of sodium sulfide and 700-800 g/t of activated carbon are simultaneously added into the copper-lead-zinc-arsenic bulk concentrate, after stirring for 8 minutes to achieve a drug removal effect, a combined inhibitor containing 800-1000 g/t of lime, 200-300 g/t of sodium humate and 600-800 g/t of bleaching powder is sequentially added, then 40-60 g/t of butyl xanthate and 10-20 g/t of pine oil are sequentially added, stirring is respectively carried out for 4 minutes, 2 minutes and 1 minute, then copper-lead-zinc and arsenic are separated, the concentrate obtained by separating the copper-lead-zinc and arsenic is the copper-lead-zinc bulk concentrate, and tailings enter copper-zinc scavenging.

Preferably, in the step S3, a combined inhibitor containing 400-600 g/t of lime, 100-200 g/t of sodium humate and 300-500 g/t of bleaching powder is sequentially added into the flotation machine, then 20-30 g/t of butyl xanthate and 5-10 g/t of pine oil are sequentially added, copper-lead-zinc scavenging is performed after stirring for 4 minutes, 2 minutes and 1 minute respectively, the scavenged middlings are returned to the copper-lead-zinc and arsenic separation operation, and the tailings are the final arsenic concentrates.

Compared with the prior art, the invention provides a flotation separation method for copper, lead, zinc and arsenic of complex polymetallic sulphide ores, which adopts a partial mixing-preferential flotation method for high-sulfur copper, lead and zinc polymetallic ores at present, and when a traditional lime, zinc sulfate and sodium sulfite combined reagent is used for inhibiting zinc-sulfur minerals, the consumption of lime is large, and fine ore particles are condensed due to the excessive consumption of lime, so that foams are sticky and even run away from a groove, and zinc floats upwards in advance due to the use of a collecting agent with poor selectivity during the partial mixing flotation of copper and lead, so that the metal content in each concentrate product is higher finally. The method breaks through the traditional alkaline system (the pH value is not less than 11), and sulfide ore flotation is carried out in a weak acid system, so that the dosage and the type of the medicament in the flotation process are greatly reduced, the multi-metal flotation process is simplified, and the subsequent process treatment capacity is reduced; the inhibitor lime, sodium humate and bleaching powder used for separating copper, lead and zinc from arsenic and the inhibitor zinc sulfate, sodium sulfite and sodium carboxymethylcellulose used for separating copper and lead and zinc have the advantages of novel combination, low medicament dosage, low price, good separation effect and the following advantages:

(1) the medicament used by the invention is a conventional beneficiation medicament, has no pollution to the environment, is low in price, is easy to purchase in the market, and is convenient for cost control;

(2) the method has good separation effect of the copper, lead, zinc and arsenic valuable elements, the obtained concentrate product has high quality, and the metal content in the concentrate product is low;

(3) the method has the advantages of stable technical indexes, comprehensive and efficient treatment and recovery of useful elements in fine-grained complex copper-lead-zinc polymetallic sulfide ores and similar ores, obvious effect and strong universal applicability. The copper grade in the obtained copper concentrate is more than 18 percent, the copper recovery rate is more than 70 percent, the lead grade in the lead-zinc bulk concentrate is more than 15, the zinc grade is more than 36, the lead and zinc grade is more than 55, and the lead and zinc recovery rates are more than 70 percent and meet the quality requirement of grade I of the industry standard (YS/T452-2002);

the reagent used in the design of the invention is a conventional beneficiation reagent, has no pollution to the environment, low price, easy acquisition in the market, convenient cost control, good separation effect of copper, lead, zinc and arsenic valuable elements, high quality of the obtained concentrate product and low metal content in the concentrate product.

Drawings

FIG. 1 is a process flow diagram of the flotation separation method of copper, lead, zinc and arsenic in complex multi-metal sulfide ores provided by the invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.