阅读说明：本技术 一种捕收剂及其制备方法和用途 (Collecting agent and preparation method and application thereof ) 是由 凌石生 李剡兵 罗科华 冯兴隆 肖巧斌 杨朝义 尚衍波 李莹 贺壮志 游乐明 杜 于 2021-09-13 设计创作，主要内容包括：本发明提供了一种捕收剂及其制备方法和用途,所述捕收剂包括N,N-二乙基二硫代氨基甲酸丙腈酯、甲基异丁基甲醇、烷基酚聚氧乙烯醚和柴油的组合。通过N,N-二乙基二硫代氨基甲酸丙腈酯、甲基异丁基甲醇、烷基酚聚氧乙烯醚和柴油复配,所述捕收剂具有优异的溶解性、分散性和流动性；对铜钼矿物的选择性好、捕收能力强,能够获得高品位和较高回收率的铜钼精矿,选矿过程中用量较少即能达到较好的浮选效果。同时,所述捕收剂的原料来源广泛、制备工艺简单,具有良好的应用前景。(The invention provides a collector and a preparation method and application thereof, wherein the collector comprises the combination of N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene ether and diesel oil. The collecting agent is compounded by N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene and diesel oil, and has excellent solubility, dispersibility and fluidity; the copper-molybdenum ore flotation method has good selectivity and strong collecting capability on copper-molybdenum ores, can obtain copper-molybdenum concentrates with high grade and high recovery rate, and can achieve good flotation effect with less consumption in the ore dressing process. Meanwhile, the collecting agent has wide raw material source, simple preparation process and good application prospect.)

1. A collector comprising a combination of propionitrile N, N-diethyldithiocarbamate, methyl isobutyl carbinol, alkylphenol ethoxylates, and diesel.

2. A collector according to claim 1, wherein the collector comprises, in parts by weight, 65-75 parts propionitrile N, N-diethyldithiocarbamate, 5-10 parts methyl isobutyl carbinol, 1-3 parts polyoxyethylene alkylphenol ether, and 20-25 parts diesel.

3. A collector as claimed in claim 1 or 2 wherein the alkylphenol ethoxylates comprise any one of or a combination of at least two of nonylphenol ethoxylates, octylphenol ethoxylates or dodecylphenol ethoxylates.

4. A collector as claimed in any one of claims 1 to 3 wherein the degree of polymerisation of the ethylene oxide in the alkylphenol ethoxylates is in the range of from 8 to 12.

5. A method of preparing the collector according to any one of claims 1 to 4, wherein the method of preparing comprises the steps of:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene ether and diesel according to the formula amount to obtain the collecting agent.

6. The method of claim 5, wherein the mixing comprises stirring.

7. The method according to claim 5 or 6, wherein the stirring time is 20 to 40 min.

8. The production method according to any one of claims 5 to 7, characterized by comprising the steps of:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl methanol and alkylphenol polyoxyethylene, adding diesel oil, and stirring for 20-40 min to obtain the collecting agent.

9. A copper molybdenum ore collector, comprising the collector of any one of claims 1 to 4.

10. Use of the collector of any one of claims 1 to 4 in a copper molybdenum ore flotation process.

Technical Field

The invention belongs to the technical field of mineral processing, and particularly relates to a collecting agent, and a preparation method and application thereof.

Background

The world has identified porphyry copper ore accounting for about 76% of the total copper, while the associated molybdenum in porphyry copper ore is an important source of molybdenum metal. With the concept of sustainable development and resource conservation, more and more people pay more attention to the efficient treatment of copper-molybdenum ores and the collection of copper-molybdenum metals.

In the prior art, a mixed flotation method is mostly adopted to treat copper-molybdenum ore, and mainly adopts medicaments such as esters (ethionamide, ester-105 and the like), xanthates (ethyl xanthate, butyl xanthate and the like), black medicaments (ammonium butyl black medicament, isobutyl sodium black medicament and the like) and hydrocarbon oils (kerosene, diesel oil and the like) as collecting agents. For example, CN108435437A discloses a low-alkalinity high-selectivity copper-molybdenum flotation collector and a preparation method thereof, the effective components of the copper-molybdenum flotation collector comprise heavy oil, thiocarbamate, hydrocarbon-oil mixture and diesel oil, and the weight ratio of each component is: 22-28 parts of heavy oil, 8-12 parts of thiocarbamate, 22-28 parts of hydrocarbon oil mixture and 35-45 parts of diesel oil. The copper-molybdenum flotation collector can realize efficient collection of copper minerals and molybdenum minerals in a low-alkalinity environment with a pH value of 7-9, is easy to sort, has strong selectivity, cannot corrode equipment, and has high popularization value and application prospect. But the recovery rate of the copper molybdenum flotation collector for copper minerals needs to be further improved.

CN101844107A discloses a combined collector for porphyry copper-molybdenum ore flotation and a flotation method thereof. The combined collecting agent at least contains phthalate and thiocarbonyl thiourea, and can be used for a molybdenum-copper floatable process mainly comprising molybdenum, so that molybdenite and part of copper sulfide minerals with good floatability are floated to obtain molybdenum-copper bulk concentrate with high molybdenum recovery rate; then strengthening and recovering the copper sulfide mineral with poor floatability. The method effectively solves the problem of strong inhibition effect of lime high-alkali environment on molybdenite in the existing mixed flotation process of porphyry copper-molybdenum ore, and has the characteristics of simple and reasonable flow, high molybdenum recovery rate and the like. However, recovery of copper cannot be achieved at the same time, and the recovery rate of copper is lowered.

The general defects of the above contents are that the floatability of copper and molybdenum is greatly different, the medicament systems of the copper and molybdenum are different, the copper and molybdenum can not be collected well in actual production, pyrite and other gangue minerals which are easy to be mixed with and have strong collecting force cause low concentrate grade, the collecting capability which is good in selectivity is weak, the recovery rate is low, and resource waste is caused.

Therefore, the research and development of a collector capable of recovering copper and molybdenum at the same time and efficiently recovering copper and molybdenum resources are problems to be solved urgently in the field.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a collector and a preparation method and application thereof. The collecting agent adopts the combination of N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene and diesel oil, has good selectivity to copper molybdenum ore and strong collecting capability, and can also recover copper molybdenum.

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

in a first aspect, the present invention provides a collector comprising a combination of propionitrile N, N-diethyldithiocarbamate, methyl isobutyl carbinol, polyoxyethylene alkylphenol ether and diesel.

According to the invention, through the synergistic use of the N, N-diethyl dithiocarbamate propionitrile ester, the methyl isobutyl carbinol, the alkylphenol polyoxyethylene and the diesel oil, the collecting agent has good selectivity on copper-molybdenum ore, can give consideration to the recovery of copper and molybdenum, and avoids the inclusion of other minerals such as pyrite and the like; the N, N-diethyl dithiocarbamate propionitrile ester has good flotation selectivity on copper sulfide, the diesel oil has good selectivity on molybdenum, the methyl isobutyl carbinol can prevent the collector from being solidified, and the alkylphenol polyoxyethylene ether can improve the fluidity, the solubility and the dispersibility of the collector, thereby being beneficial to the flotation of copper and molybdenum minerals.

According to the preferable technical scheme, the collecting agent comprises 65-75 parts by weight of N, N-diethyl dithiocarbamate propionitrile ester, 5-10 parts by weight of methyl isobutyl carbinol, 1-3 parts by weight of alkylphenol polyoxyethylene ether and 20-25 parts by weight of diesel oil.

Preferably, the collector comprises 65-75 parts by weight of N, N-diethyldithiocarbamate propionitrile ester, which may be, for example, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, and the like.

In the invention, the weight part of the N, N-diethyl dithiocarbamate propionitrile ester is less than 65 parts, the collecting capability is weakened, and the recovery rate of copper-molybdenum concentrate is reduced; and if the amount of the collector is more than 75 parts, the solubility, the flowability and the dispersibility of the collector are poor, and the recovery of copper-molybdenum concentrate is not facilitated.

Preferably, the collector comprises 5-10 parts by weight of methyl isobutyl carbinol, and can be, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, and the like.

In the invention, the methyl isobutyl carbinol accounts for less than 5 parts by weight, so that the dissolubility, the fluidity and the dispersibility of the collecting agent are poor; if the amount is more than 10 parts, the proportion of other components is reduced, and the collecting capability is weakened.

Preferably, the collector comprises 1-3 parts of alkylphenol polyoxyethylene ether by weight, and can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts and the like.

In the invention, the alkylphenol polyoxyethylene ether is less than 1 part by weight, and the dissolubility, the fluidity and the dispersibility of the collecting agent are poor; more than 3 portions results in large amount of flotation froth and difficult control of the flotation process.

Preferably, the collector comprises 20-25 parts by weight of diesel oil, for example, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts and the like.

In the invention, the diesel oil is less than 20 parts, the dissolubility, the fluidity and the dispersibility of the collecting agent are deteriorated, and the recovery rate of molybdenum is low; more than 25 parts, the foam is fragile and the collecting ability is weakened.

Preferably, the alkylphenol ethoxylate comprises any one of nonylphenol ethoxylate, octylphenol ethoxylate or dodecylphenol ethoxylate or a combination of at least two thereof.

Preferably, the polymerization degree of ethylene oxide in the alkylphenol ethoxylate is 8 to 12, and may be, for example, 8, 9, 10, 11, 12, or the like.

In a second aspect, the present invention provides a method of preparing a collector as described in the first aspect, the method comprising the steps of:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene ether and diesel according to the formula amount to obtain the collecting agent.

Preferably, said mixing comprises stirring.

Preferably, the stirring time is 20-40 min, for example, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min, etc.

As a preferred technical scheme of the invention, the preparation method comprises the following steps:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl methanol and alkylphenol polyoxyethylene, adding diesel oil, and stirring for 20-40 min to obtain the collecting agent.

In a third aspect, the present invention provides a copper molybdenum ore collector comprising a collector as described in the first aspect.

In a fourth aspect, the present invention provides the use of a collector according to the first aspect in a copper molybdenum ore flotation process.

The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.

Compared with the prior art, the invention has the beneficial effects that:

the collecting agent provided by the invention has the advantages that through the synergistic effect of N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene ether and diesel oil, the prepared collecting agent has high selectivity on copper-molybdenum ore and strong collecting capability, and can collect copper and molybdenum at the same time, the copper grade in copper-molybdenum concentrate is more than 24%, the molybdenum grade is not less than 0.42%, the copper recovery rate is more than 88%, and the molybdenum recovery rate is more than 72%.

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.

Example 1

The invention provides a collector which comprises 72 parts of N, N-diethyl dithiocarbamate propionitrile ester, 8 parts of methyl isobutyl carbinol, 1 part of alkylphenol polyoxyethylene ether (NP-10) and 23 parts of diesel.

The invention provides a preparation method of a collecting agent, which comprises the following specific steps:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) at normal temperature and normal pressure according to the formula amount, adding diesel oil, and stirring for 30min to obtain the collecting agent.

Example 2

The invention provides a collector which comprises 70 parts of N, N-diethyl dithiocarbamate propionitrile ester, 9 parts of methyl isobutyl carbinol, 1.5 parts of alkylphenol polyoxyethylene ether (NP-10) and 25 parts of diesel.

The invention provides a preparation method of a collecting agent, which comprises the following specific steps:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) at normal temperature and normal pressure according to the formula amount, adding diesel oil, and stirring for 20min to obtain the collecting agent.

Example 3

The invention provides a collector which comprises 75 parts of N, N-diethyl dithiocarbamate propionitrile ester, 10 parts of methyl isobutyl carbinol, 1 part of alkylphenol polyoxyethylene ether (NP-10) and 20 parts of diesel.

The invention provides a preparation method of a collecting agent, which comprises the following specific steps:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) at normal temperature and normal pressure according to the formula amount, adding diesel oil, and stirring for 25min to obtain the collecting agent.

Example 4

The invention provides a collector which comprises 65 parts of N, N-diethyl dithiocarbamate propionitrile ester, 5 parts of methyl isobutyl carbinol, 3 parts of alkylphenol polyoxyethylene ether (OP-8) and 20 parts of diesel.

The invention provides a preparation method of a collecting agent, which comprises the following specific steps:

mixing N, N-diethyl dithiocarbamic acid propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene ether (OP-8) at normal temperature and normal pressure according to the formula amount, adding diesel oil, and stirring for 40min to obtain the collecting agent.

Example 5

The present invention provides a collector which differs from example 1 only in that the part by weight of N, N-diethyldithiocarbamate propionitrile ester in the collector is greater than 75 parts; other components and amounts were the same as in example 1. The collecting agent comprises 80 parts of N, N-diethyl dithiocarbamate propionitrile ester, 8 parts of methyl isobutyl carbinol, 1 part of alkylphenol polyoxyethylene ether (NP-10) and 23 parts of diesel.

The invention provides a preparation method of a collecting agent, which comprises the following specific steps:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) at normal temperature and normal pressure according to the formula amount, adding diesel oil, and stirring for 30min to obtain the collecting agent.

Example 6

The present invention provides a collector which differs from example 1 only in that the part by weight of methyl isobutyl carbinol in the collector is greater than 10 parts; other components and amounts were the same as in example 1. The collecting agent comprises 72 parts of N, N-diethyl dithiocarbamate propionitrile ester, 15 parts of methyl isobutyl carbinol, 1 part of alkylphenol polyoxyethylene ether (NP-10) and 23 parts of diesel oil.

The invention provides a preparation method of a collecting agent, which comprises the following specific steps:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) at normal temperature and normal pressure according to the formula amount, adding diesel oil, and stirring for 30min to obtain the collecting agent.

Example 7

The invention provides a collector which is different from the collector in example 1 only in that the part by weight of alkylphenol ethoxylates in the collector is more than 3 parts; other components and amounts were the same as in example 1. The collecting agent comprises 72 parts of N, N-diethyl dithiocarbamate propionitrile ester, 8 parts of methyl isobutyl carbinol, 5 parts of alkylphenol polyoxyethylene ether (NP-10) and 23 parts of diesel oil.

The invention provides a preparation method of a collecting agent, which comprises the following specific steps:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) at normal temperature and normal pressure according to the formula amount, adding diesel oil, and stirring for 30min to obtain the collecting agent.

Example 8

The invention provides a collector which differs from example 1 only in that the part by weight of diesel in the collector is greater than 25 parts; other components and amounts were the same as in example 1. The collecting agent comprises 72 parts of N, N-diethyl dithiocarbamate propionitrile ester, 8 parts of methyl isobutyl carbinol, 1 part of alkylphenol polyoxyethylene ether (NP-10) and 30 parts of diesel oil.

The invention provides a preparation method of a collecting agent, which comprises the following specific steps:

mixing N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol and alkylphenol polyoxyethylene (NP-10) at normal temperature and normal pressure according to the formula amount, adding diesel oil, and stirring for 30min to obtain the collecting agent.

Comparative example 1

This comparative example provides a collector which differs from example 1 only in the absence of diesel in the collector; the other components and amounts were the same as in example 1.

The present comparative example provides a method of preparing a collector, the specific steps being the same as example 1.

Comparative example 2

This comparative example provides a collector which differs from example 1 only in that there is no methyl isobutyl carbinol in the collector; the other components and amounts were the same as in example 1.

The present comparative example provides a method of preparing a collector, the specific steps being the same as example 1.

Comparative example 3

This comparative example provides a collector that differs from example 1 only in the absence of alkylphenol ethoxylates (NP-10) in the collector; the other components and amounts were the same as in example 1.

The present comparative example provides a method of preparing a collector, the specific steps being the same as example 1.

Comparative example 4

This comparative example provides a collector that differs from example 1 only in that 72 parts of propionitrile N, N-diethyldithiocarbamate are replaced with 72 parts of ethionamide in the collector; the other components and amounts were the same as in example 1.

The present comparative example provides a method of preparing a collector, the specific steps being the same as example 1.

Comparative example 5

This comparative example provides a collector which differs from example 1 only in that 8 parts of methyl isobutyl carbinol are replaced by 8 parts of alpha-terpene alcohol; the other components and amounts were the same as in example 1.

The present comparative example provides a method of preparing a collector, the specific steps being the same as example 1.

Comparative example 6

This comparative example provides a collector which differs from example 1 only in that 1 part of alkylphenol ethoxylate (NP-10) is replaced by 1 part of fatty alcohol ethoxylate; the other components and amounts were the same as in example 1.

The present comparative example provides a method of preparing a collector, the specific steps being the same as example 1.

Comparative example 7

This comparative example provides a collector which differs from example 1 only in that 23 parts of diesel oil are replaced by 23 parts of kerosene; the other components and amounts were the same as in example 1.

The present comparative example provides a method of preparing a collector, the specific steps being the same as example 1.

Comparative example 8

The present comparative example provides a collector, which is butyl xanthate.

Comparative example 9

This comparative example provides a collector, which is kerosene.

The collector provided by the embodiment and the comparative example of the invention is used for testing the flotation performance of copper-molybdenum ore: grinding a certain copper-molybdenum ore (the Cu content is 0.56 percent and the Mo content is 0.012 percent) to the mass percentage of 63 percent of a-0.074 mm grade material, and then adding a pH regulator, a collecting agent and a foaming agent to carry out primary roughing, secondary scavenging and tertiary concentration treatment, wherein during concentration, the coarse concentrate is ground to the mass percentage of 90 percent of the-0.045 mm grade material.

The specific test results are shown in table 1:

TABLE 1

From the above table, the collector provided by the invention can recover copper and molybdenum at the same time by compounding N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene ether and diesel oil. Under the condition of ensuring high copper grade and copper recovery rate, the molybdenum grade in the copper-molybdenum concentrate is more than or equal to 0.42 percent, and the molybdenum recovery rate is more than 72 percent.

As is clear from comparison of examples 1 to 4 with examples 5 to 8, it is found that propionitrile N, N-diethyldithiocarbamate, methyl isobutyl carbinol, alkylphenol ethoxylates and diesel oil have a higher effect of recovering copper-molybdenum ore within a specific content range.

Compared with the conventional collecting agent, the collecting agent adopts the combination of N, N-diethyl dithiocarbamate propionitrile ester, methyl isobutyl carbinol, alkylphenol polyoxyethylene ether and diesel oil, and the grade and recovery rate of copper and molybdenum in copper and molybdenum concentrate obtained by flotation are improved. When a certain component is removed or replaced by other agents, the grade of copper and molybdenum or the recovery rate of copper and molybdenum in the copper and molybdenum concentrate is reduced.

In conclusion, the collector provided by the invention has the advantages that the specific proportion is formed by the N, N-diethyl dithiocarbamic acid propionitrile ester, the methyl isobutyl carbinol, the alkylphenol polyoxyethylene ether and the diesel oil, the recovery of copper and molybdenum can be considered, the grade and the recovery rate of copper and molybdenum are improved, the raw material source is wide, the preparation process is simple, and the application prospect is good.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.