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WO2021052002A1 - Procédé de préparation d'un agent de collecte de sulfure de cuivre - Google Patents

Procédé de préparation d'un agent de collecte de sulfure de cuivre Download PDF

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Publication number
WO2021052002A1
WO2021052002A1 PCT/CN2020/104032 CN2020104032W WO2021052002A1 WO 2021052002 A1 WO2021052002 A1 WO 2021052002A1 CN 2020104032 W CN2020104032 W CN 2020104032W WO 2021052002 A1 WO2021052002 A1 WO 2021052002A1
Authority
WO
WIPO (PCT)
Prior art keywords
xanthate
copper
sodium
dichloroalkane
copper sulfide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2020/104032
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English (en)
Chinese (zh)
Inventor
迟晓鹏
郭芸杉
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Fuzhou University
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Fuzhou University
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Filing date
Publication date
Application filed by Fuzhou University filed Critical Fuzhou University
Publication of WO2021052002A1 publication Critical patent/WO2021052002A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/018—Mixtures of inorganic and organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores

Definitions

  • the invention belongs to the technical field of organic medicament synthesis, and specifically relates to a preparation method of a copper sulfide collector.
  • the characteristic of the sulfide ore collector is that the molecule contains sulfur atoms that can collect sulfide minerals. It has no effect on gangue minerals, such as quartz and calcite. Therefore, this type of collector is used for flotation of sulfide ore. It is easy to separate and remove gangue such as quartz and calcite.
  • Sulfide ore collectors can be divided into two types according to their types. One is soluble in water and ionizes anions containing sulfur atoms. This anion has a collection effect on sulfide minerals. It is an anionic collector, such as xanthate and black medicine. , Sulfur nitrogen, etc.; the other is a polar oil compound that cannot be ionized in water. They are derivatives of xanthate, black medicine, sulfur nitrogen, such as double xanthate, xanthate, thiourethane, double black Generally speaking, the collection capacity of medicine and black medicine esters is weaker than that of xanthate, but the selectivity is better.
  • the flotation mainly uses xanthate and black medicine sulfide ore collectors.
  • Copper smelting slag contains a lot of sulfide minerals, but when these collectors are used in the flotation process of copper smelting slag, due to the weak selectivity, the flotation effect is often not ideal, and the resulting concentrate product contains A large number of other mineral components make the quality of the obtained flotation product poor, and also make it more difficult to carry out the further copper extraction process.
  • the use of other relatively selective flotation reagents such as thiourethane, black medicine ester, thionitrate, etc., has the problem of excessively high medicament cost.
  • the main purpose of the present invention is to provide a method for preparing copper sulfide collectors to solve the problem that the conventional collectors for flotation of copper sulfide ore are relatively weak in selectivity, and at the same time, the cost of chemicals is high, and it is difficult to achieve copper and copper smelting.
  • the separation of arsenic, sulfur and other elements makes the flotation process of copper smelting slag too long.
  • a preparation method of copper sulfide collector which comprises the following steps:
  • step (3) After the reaction is over, transfer the material liquid obtained in step (2) to a separatory funnel and let stand still, and wash the organic layer with distilled water for more than 3 times;
  • step (3) Add anhydrous magnesium sulfate to the cleaned product in step (3), dry it, and filter to obtain an oily final product.
  • the dichloroalkane used is dichloroethane, 1,1-dichloroethane, dichloropropane, 1,1-dichloropropane, dichlorobutane, 1,1-dichlorobutane, dichloropropane Isobutane, 1,1-dichloroisobutane, dichloropentane, 1,1-dichloropentane, dichloroisopentane, 1,1-dichloroisopentane, dichloroneopentane, Any one of 1,1-dichloroneopentane;
  • the xanthates used are sodium ethyl xanthate, sodium propyl xanthate, sodium butyl xanthate, sodium isobutyl xanthate, sodium amyl xanthate, sodium isoamyl xanthate, One of the sodium neopentyl xanthate.
  • the molar ratio of xanthate to dichloroalkane is 1:1.
  • the dichloroalkane used can be any alkane containing two chlorines. Considering the solubility of the synthetic collector, try to use dichloroalkane with less carbon chain.
  • step (1) the heating temperature of the water bath is 40 ⁇ 70°C, the stirring speed is 250r/min, and the heating time is 30 ⁇ 60min.
  • step (2) the dropping rate of the dichloroalkane is 1 to 2 drops/s, so as not to be too violent to make the temperature uncontrollable.
  • step (2) the reaction is controlled at 25-70°C, and the reaction time is controlled at 6-24h.
  • the standing time in step (3) is 5 ⁇ 6h.
  • the drying temperature in step (4) is 50 ⁇ 80°C, and the time is 12 ⁇ 14h.
  • the beneficial technical effects of the present invention are: the preparation process conditions of the collector of the present invention are simple and easy to operate, and the obtained collector structure contains one -OCSS- group, which is applied to copper smelting During the flotation of slag, the flotation separation of copper, sulfur and arsenic in copper sulfide ore can be realized, so that the copper in the copper slag can be efficiently recovered, so that the content of arsenic and other elements in the flotation concentrate can be controlled, and the content of copper can be increased. The quality of smelting slag flotation products.
  • Figure 1 is an infrared spectrogram of the collector prepared in Example 1;
  • Figure 2 is an infrared spectrogram of the collector prepared in Example 2;
  • FIG. 3 is an infrared spectrum diagram of the collector prepared in Example 3.
  • the invention provides a method for preparing a collector for copper sulfide ore, which comprises the following steps:
  • R and R / are each independently selected from C 2 -C 5 alkyl groups, such as ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, neopentyl;
  • reaction product Since the drug obtained by the reaction also contains a large amount of xanthate, solvent absolute ethanol or distilled water, and NaCl generated by the reaction, the reaction product needs to be transferred to a separatory funnel and allowed to stand for a period of time to make the reaction Products and excess reactants can be separated as much as possible;
  • step (1) the heating temperature of the water bath is 40 ⁇ 70°C. If the temperature is too high, the structure of xanthate will be changed, which will not ensure the accuracy of the experiment. If the temperature is too low, the xanthate will be reduced.
  • the dissolution rate Stirring can accelerate the dissolution of xanthogenate and make the dissolution of xanthogen acid more complete, so set the stirring speed of the stirrer to 250r/min, and the heating time is determined by the dissolution of xanthogenate, generally 30 ⁇ 60min.
  • step (2) considering the solubility of the final synthesized collector, the added dichloroalkane contains as few carbon chains as possible.
  • step (2) since the reaction is an exothermic reaction, when adding dichloroalkane, the dropping rate of dichloroalkane should be controlled at 1 ⁇ 2 drops/sec as much as possible to avoid the reaction being too violent. As a result, the temperature is not controlled, and the reaction cannot be well detected.
  • the reaction temperature should be controlled at 25-70°C as far as possible. If the temperature is too high, the reaction will generate a large amount of by-products, thereby reducing the yield of the target product, while the temperature is too low and the reaction will not proceed normally.
  • the reaction time is generally controlled at 6 ⁇ 24h, and the reaction time can be appropriately extended to make the reaction proceed more thoroughly.
  • the dichloroalkane used is dichloroethane, 1,1-dichloroethane, dichloropropane, 1,1-dichloropropane, dichlorobutane, 1,1-dichlorobutane, dichloroisobutyl Alkane, 1,1-dichloroisobutane, dichloropentane, 1,1-dichloropentane, dichloroisopentane, 1,1-dichloroisopentane, dichloroneopentane, 1, Any one of 1-dichloroneopentane;
  • the xanthates used are sodium ethyl xanthate, sodium propyl xanthate, sodium butyl xanthate, sodium isobutyl xanthate, pentyl One of sodium xanthate, sodium isoamyl xanthate, sodium neopentyl xanthate; in step (2), the mass ratio of x
  • the standing time is 5 ⁇ 6h.
  • the purpose of standing is to make the product and other ingredients separate naturally as much as possible.
  • the standing time can be adjusted according to the actual situation; after liquid separation, use distilled water Clean the oil layer more than 3 times to ensure the purity of the product as much as possible.
  • step (4) after the product is washed with distilled water, a large amount of distilled water will remain in the oil layer. Therefore, the desiccant anhydrous magnesium sulfate is added to the oil layer for treatment.
  • the amount of anhydrous magnesium sulfate added depends on the actual situation. It is usually added until anhydrous magnesium carbonate powder appears in the oil layer and no longer dissolves.
  • step (4) after adding anhydrous magnesium carbonate, the oil layer needs to be filtered and heated.
  • the drying temperature is 50 ⁇ 80°C
  • the drying time is generally 12 ⁇ 14h
  • the drying time can be appropriately extended. After drying, the resulting product needs to be filtered to obtain a final product with higher purity.
  • the copper content is 4.56%, and the copper slag with a particle size of 0.30mm or less accounts for 95%.
  • the copper recovery rate reached 82.37%, and the copper concentrate grade reached 23.84%.
  • the copper recovery rate was 83.63%, and the copper concentrate grade was 16.34%.
  • the copper content is 0.38%
  • the regrinding particle size of the concentrate is -0.038mm accounting for 78%, three times of selection and two sweeps.
  • the copper recovery rate reached 80.70%
  • the copper concentrate grade reached 37.02%.
  • the recovery rate of copper is 80.74%
  • the grade of copper concentrate is 19.88%.
  • the copper content is 0.38%, and the copper ore with a particle size of -0.074mm or less accounts for 58%.
  • the recovery rate of copper after two roughings, one beneficiation and three sweepings reached 71.30%, and the copper concentrate grade reached 41.50%.
  • the recovery rate of copper is 73.73%, and the grade of copper concentrate is 18.46%.
  • the synthesized agent is a lipid collector.
  • the absorption peaks of CH3 symmetrical bending vibration and asymmetrical bending vibration at 1367.6cm-1 and 1463.3cm-1 are respectively.
  • 2868.1cm-1 and 2955.1 cm-1 is the absorption peak of symmetric bending vibration and asymmetric bending vibration of CH2, 1133.5 cm-1 and 1226.3 cm-1 are the COC asymmetric stretching vibration absorption peaks
  • 682.4 cm-1 is the C-Cl bond stretching vibration absorption peak
  • the preparation process conditions of the collector of the present invention are simple and easy to operate. When it is applied to the flotation of copper sulfide ore, it can realize the flotation separation of copper, arsenic and sulfur in the copper sulfide ore, so that the copper in the copper slag can be efficiently obtained. Recycling can control the arsenic content in the flotation concentrate product and improve the quality of the flotation product of copper smelting slag.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un agent de collecte de sulfure de cuivre. Le procédé consiste à placer le xanthogénate dans de l'eau distillée ou de l'éthanol anhydre pour le chauffage et la dissolution, puis à ajouter du dichloroalcane pour la réaction, à prendre une couche d'huile, à laver la couche d'huile avec de l'eau distillée, puis à sécher la couche d'huile lavée pour obtenir l'agent collecteur de sulfure de cuivre. L'agent de collecte préparé peut permettre l'extraction du cuivre dans un puits de sulfure de cuivre, peut réduire la collecte de pyrite et d'autres minéraux de gangue le plus possible, et permet d'obtenir l'augmentation du taux de récupération de cuivre dans des minerais de sulfure de cuivre dans une large mesure. De plus, l'agent de collecte présente un faible coût, est simple à mettre en œuvre, et peut réduire le coût d'investissement du procédé de flottation.
PCT/CN2020/104032 2019-09-20 2020-07-24 Procédé de préparation d'un agent de collecte de sulfure de cuivre Ceased WO2021052002A1 (fr)

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CN201910893904.4A CN110560271A (zh) 2019-09-20 2019-09-20 一种硫化铜捕收剂的制备方法
CN201910893904.4 2019-09-20

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CN110560271A (zh) * 2019-09-20 2019-12-13 福州大学 一种硫化铜捕收剂的制备方法
CN111346738B (zh) * 2020-04-02 2021-11-16 紫金矿业集团股份有限公司 一种s-烷氧烷基酯类捕收剂及其制备和应用

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CN101321588A (zh) * 2005-11-22 2008-12-10 巴里·格雷厄姆·拉姆斯登 提高矿石中矿物的回收率
CN103977907A (zh) * 2014-05-15 2014-08-13 中南大学 一种黄原酸酰基酯捕收剂及其制备和应用方法
CN109794358A (zh) * 2019-03-22 2019-05-24 福州大学 一种用于铜冶炼渣的捕收剂的制备方法
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CN1215909C (zh) * 2002-12-09 2005-08-24 昆明冶研新材料股份有限公司 一种浮选硫化铜矿石的捕收剂
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CN101321588A (zh) * 2005-11-22 2008-12-10 巴里·格雷厄姆·拉姆斯登 提高矿石中矿物的回收率
CN103977907A (zh) * 2014-05-15 2014-08-13 中南大学 一种黄原酸酰基酯捕收剂及其制备和应用方法
CN109794358A (zh) * 2019-03-22 2019-05-24 福州大学 一种用于铜冶炼渣的捕收剂的制备方法
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