Combination of collectors

    Oil collectors are rarely used at present, but as a historical development process, it is the incubation period of combination drugs, and its practice and development provide inspiration for future combination drugs.
    As a major breakthrough in the field of 1924 ~ 1926 flotation agents, soaps collector (1924), xanthate collector (1925) and dithio phosphate collector (1926) type plasma With the advent of collectors, the combined use of ionic collectors and hydrocarbon oils has increased, and the combined use of collectors has also begun to move from the spontaneous phase to the conscious phase. In the early 1930s, when soap was used to float apatite, the use of fuel oil as an additive reduced excessive foaming and increased flotation index. When xanthate flotation of lead and copper sulfide ore, adding a hydrocarbon oil may be strengthened and the metal ore flotation coarse ore gangue even the living body and, after the hydrocarbon oil collector in combination with an ionic increased, still the catch The combination of collection and use uses one aspect of research and application.
    From the 1940s to the early 1950s, the combination of ionic collectors became the dominant aspect of the combined use of collectors. 1957 Stockholm International Conference on Mineral Processing格林博茨基report presented a summary of catch in the use of a combination of collectors, when the US reported 29 lead zinc ore concentrator in seven processing plant, are used Combined collectors, 2 to 5 of the 22 copper selection plants use combined collectors. Combined collectors have also been applied to copper-selected plants in the former Soviet Union. The report also systematically introduced the test results of their use of different xanthate, combined flotation sulfide or yellow sulphate and sodium oleate combined flotation oxidized sulphide ore, and the isotope tracer method was used to determine the adsorption capacity of the agent. The relationship between recovery rates and the use of advanced electronic instruments to measure contact time to study the effect of combination drugs on the rate of adsorption. The presentation of this report has aroused widespread interest in the use of collector combinations and has facilitated the development of combination drug research and applications.
    In the past 30 years, the combination of pharmaceuticals has entered a stage of vigorous development and has the following characteristics:
    (1) The combination of flotation agents is used more and more widely, from the combination of collectors to the combination of inhibitors, the combination of foaming agents, the combination of flocculants, and the combination of collectors and The application is the most, followed by the inhibitor. The combination system has also evolved from a binary combination system to a multi-component system, and the type of the pharmaceutical combination has also been developed from the combination of the same type of similar agents to the combination of the use of the heterogeneous agents and the combination of the shaped agents.
    According to the statistics of 59 non-ferrous metal selection plants in Northeast China Institute of Technology (now Northeastern University) in 1976, 33 collectors were used alone, and 26 were used in combination, accounting for 44% of the total number of selected plants.
    In 1978, the British Mining Journal reported statistics on dozens of copper sulphide and copper and molybdenum plants. The plant used in the combination of foaming agents accounted for 26% in 1960 and 41% in 1975.
    According to the survey of the fifth annual mineral processing pharmacy evaluation report of China, a total of 81 combinations of combination agents in 1986 and 1987, of which 58 were collectors, accounting for 72%; 19 were inhibitors, accounting for 23%; Three combinations of agents, accounting for 4%; one flocculant combination. Among the 81 combinations, the binary combination is 73%, 90%, and the ternary combination is 8%, of which 4 are collectors and inhibitors. In the collector combination, most of them are In addition to the combination of anionic and anionic combinations of the same type of collector, the number of anionic and nonionic, anionic and nonpolar, and anionic and cationic isoforms is nearly 10%.
    (2) The proportion of patents for combined pharmaceuticals is quite large. Among the 81 combinations mentioned above, there are 27 patents, accounting for 33%. Among the 58 collector combinations, 23 are patents, accounting for about 40%. The author of this book counts the literature on flotation reagents of the former Soviet Union Mining Digests from 1977 to 1984, in which the patent volume accounts for about 42%, that is, the patent weight of the collector combination is close to the patent weight of the entire flotation agent research.
    (3) The combination drug product appears, that is, the manufacturer combines certain drugs into a mixture product in a certain proportion, for example, the Aerofloat 208 agent is a combination of ethyl sodium black drug and sec-butyl sodium black drug in a 1:1 combination. The drug, Ucon290 agent is a mixture of 75% MIBC and 25% Erophorus-65.
    Based on the above aspects, there are many combinations of drugs, which are difficult to enumerate one by one, and can only be classified as examples.
    The combination of collectors is the most used type of flotation agent, and the statistics of Table 1, Table 2, and Table 3 fully demonstrate the wide range and combination of them. Table 4, Table 5, Table 6 and the following figure are combined collector flotation non-ferrous metal sulfide ore (copper ore), rare metal ore (tungsten ore), industrial mineral (phosphorus ore) and non-metallic ore (hornblende) Illustrative results. Among them, when flotation hornblende is octadecylamine as the main collector, other agents such as distilled tar oil (M II TM), oleic acid, sodium oleate, sodium salicylate, butanol, octanol, etc. Both are added as organic additives and can be considered as another type of combination. [next]

    Table 1 Collection table of collector combinations

    Mixed system
    Mixed combination type
    symbol
    Example
    Binary combination system
    different
    type
    group
    Combined
    body
    system
    Anionic + cationic
    Anionic + nonionic
    Anionic + non-polar
    Cationic + nonionic
    Cationic + non-polar
    Non-ionic + non-polar
    AiCi
    AiNi
    AiNp
    CiNi
    CiNp
    NiNp
    Ammonia combined with advanced xanthate flotation zinc oxide ore
    Yellow or black medicine combined with Z-200 flotation copper sulfide ore
    Combination of xanthate and hydrocarbon oil flotation copper molybdenum ore
    Amine and hydrocarbon oil combination flotation potassium salt
    Combination of xanthate and hydrocarbon oil flotation copper molybdenum ore
    Homotype heterogeneous combination system
    Anionic + anionic
    Cationic + cationic
    Non-ionic + non-ionic
    Non-polar + non-polar
    AiAi'
    CiCi'
    NiNi'
    NpNp'
    Yellow medicine and black medicine combination flotation gold-bearing sulfide
    Fatty amine combined with ether amine flotation silicate
    Flotation of copper sulfide with ethyl xanthate ethyl formate and Z-200
    Petroleum , shale oil, diesel combination flotation stibnite
    Homomorphic combination system
    Anionic + anionic
    Cationic + cationic
    Non-ionic + non-ionic
    Non-polar + non-polar
    AiAi
    CiCi
    NiNi
    NpNp
    Tall oil soap and paraffin oxide iron ore flotation compositions
    Flotation quartz with high boiling point fatty amine and low boiling point fatty amine
    Float copper ore with different viscosity of similar hydrocarbon oil
    Multivariate combination system
    Ternary heterogeneous combination system
    Ternary homogeneous combination system
    Ternary heterogeneous and homotypic combination system
    AiCiNp
    AiAiAi
    AiAiAi
    Primary amines with a fatty acid composition of oil and coal flotation of nickel
    Yellow medicine combined with black medicine and HM-50 flotation nickel ore
    Yellow medicine combined with black medicine and Z-200 flotation copper sulfide ore
    Table 2   Anion collector combination classification example table

    category
    Pharmacy combination
    Instance
    Similar combination
    Xanthate + xanthate
    Black medicine + black medicine
    Mercaptans + mercaptans
    Alkyl sulfonates + alkyl sulfonates
    Carboxylic acid + carboxylic acid
    Hydroxamic acid + hydroxamic acid
    Organic tanic acid + organic tannin
    Organic phosphonic acid + organic phosphonic acid
    Flotation of copper sulfide with butyl xanthate and isobutyl xanthate
    Black # 25 drugs and drug combinations aniline black lead sulfide flotation
    Flotation gold ore combined with dodecyl mercaptan and imidazole mercaptan
    Flotation iron ore with water-soluble petroleum sulfonic acid and oil-soluble petroleum sulfonic acid
    Flotation zircon in combination with sodium oleate and stearic acid
    C 7-9 hydroxamic acid and hydroxamic acid tall oil composition cassiterite flotation
    Flotation cassiterite combined with p-toluic acid and o-toluene decanoic acid
    Phosphate and Phosphate Combination Flotation Separation of Phosphate Ore and Carbonate Ore
    Heterogeneous combination
    Xanthate + black medicine
    Xanthate + thiol
    Xanthate + carboxylic acid
    Xanthate + alkyl sulfonate
    Xanthate + Hydroxamic acid
    Xanthate + organic tannin
    Xanthate + organic phosphonic acid
    Carboxylic acid + hydroxyalkyl sulfonate
    Carboxylic acid + hydroxamic acid
    Carboxylic acid + organic tannin
    Carboxylic acid + organic phosphonic acid
    Carboxylic acid + black medicine
    Carboxylic acid + mercaptan
    Flotation copper-nickel ore combined with butyl xanthate and butyl black drug
    Combination of xanthate and dodecyl mercaptan flotation copper-nickel ore
    Flotation of copper oxide with butyl xanthate and lower fatty acid
    Flotation of copper sulfide with butyl xanthate and sodium alkylbenzene sulfonate
    Xanthate and /HM-50 combined flotation copper oxide
    Flotation tungsten ore with xanthate and benzyl phthalic acid
    Oleic acid and alkyl sulfonate combined flotation lead oxide ore
    Flotation of andalusite in combination with sodium oleate and hydroxamic acid
    Benzyl phthalic acid% oxidized paraffin soap flotation cassiterite
    Flotation of cassiterite with 1-hydroxy-octyl-1,1-bisphosphonic acid and fatty acid
    Flotation of copper oxide ore with butyl ammonium black drug and oxidized paraffin soap
    Heterogeneous combination
    Black medicine + thiol
    Black medicine + alkyl sulfonate
    Black medicine + hydroxamic acid
    Black medicine + organic tannins
    Black medicine + organic phosphonic acid
    Thiols + alkyl sulfonates
    Mercaptans + organic tannins
    Mercaptans + organic phosphonic acids
    Thiols + hydroxamic acids
    Combination of black medicine and mercaptobenzothiazole flotation copper, lead and zinc ore
    Fluorinated oxidizing agent combined with butyl ammonium black drug and C 7 - 9 hydroxamic acid
    Alkyl sulfonates + hydroxamic acids
    Combination of hydroxamic acid with alkyl sulfonate (and non-polar oil) flotation phosphate rock
    Alkyl sulfonates + organic phthalic acids
    Alkyl sulfonates + organic phosphonic acids
    Flotation cassiterite combined with toluene acid (with kerosene) and alkyl sulfonate
    Hydroxamic acid + organic tannic acid
    Hydroxamic acid + organic phosphonic acid
    Organic tanic acid + organic phosphonic acid
    Flotation cassiterite in combination with p-toluic acid and p-ethylbenzenephosphonic acid
    [next]
    Table 3   Collector combination example statistics

    Combination agent
    Number of instances
    /a
    Distribution rate
    /%
    Sulfide ore collector combination
    190
    Xanthate + xanthate
    Black medicine + black medicine
    Xanthate + black medicine
    Xanthate + ionic sulfhydryl
    Black medicine + ionic sulfhydryl
    Xanthate + sulfur-containing non-ionic (polar) type
    Black medicine + sulfur-containing non-ionic (polar) type
    Sulfur-containing nonionic (polar) type + sulfur-containing nonionic (polar) type
    Mercaptans + mercaptans, mercaptans, thirteen thiocarbonates or xanthates
    Xanthate + hydrocarbon
    Black medicine + hydrocarbon
    Xanthate + fatty acids
    Xanthate + alkyl sulfonic acid
    Xanthate (+ black medicine) + hydroxamic acid
    Other: sulfur-containing nonionic polar type + hydrocarbon or mercaptan
    Fatty acid + amine or sulfonate, thiol + phenol oil, etc.
    39
    4
    37
    12
    2
    38
    6
    3
    4
    twenty four
    3
    4
    3
    5
    6
    20.5
    2.1
    19.5
    6.3
    1.1
    20.0
    3.2
    1.6
    2.1
    12.6
    1.6
    2.1
    1.6
    2.6
    3.2
    Non-ferrous metal oxide ore collector combination
    53
    Xanthate (+ black medicine) + chelation reagent
    Xanthate (+ black medicine) + hydroxamic acid
    Chelating Reagents + Hydrocarbons
    Hydroxamic acid + hydrocarbons, xanthate + hydrocarbons (or added fatty acids)
    Xanthate + fatty acids
    Xanthate + black medicine (or thiol)
    9
    11
    7
    3
    6
    6
    17.0
    20.8
    13.2
    5.7
    11.3
    11.3
    Non-ferrous metal oxide ore collector combination
    53
    Hydroxamic acid + fatty acid (or plus xanthate)
    Xanthate + amine
    Amine + amine, amine + fatty acid
    Other: chelating agent + chelating agent, oleic acid + petroleum sulfonic acid, etc.
    2
    3
    2
    4
    3.8
    5.7
    3.8
    7.5
    Rare metal ore collector combination
    47
    Fatty acids + fatty acids
    Fatty acids + amines
    Fatty acids + hydrocarbons
    Fatty acids + organic phosphates
    Fatty acids + organic tannins
    Hydroxamic acid + chelating reagent
    Organic tanic acid + hydrocarbon
    Hydroxamic acid + hydrocarbon
    Organic decanoic acid + organic citric acid, organic phosphonic acid + organic phosphonic acid
    Organic decanoic acid + organic phosphonic acid
    Other: organic phosphonic acid + xanthate (thiourea), etc.
    12
    6
    7
    4
    5
    2
    2
    2
    3
    4
    25.5
    12.8
    14.9
    8.5
    10.6
    4.3
    4.3
    4.3
    6.4
    8.5
    Ferrous metal ore and non-metallic mineral collector combination
    148
    Fatty acids + fatty acids
    Fatty acid + (sulfonated, sulfated, halogenated) fatty acids
    Fatty acid (+ fatty acid) + adjuvant
    Fatty acid (+ fatty acid) + hydrocarbon
    Fatty acid + amine
    Fatty acid + hydroxamic acid
    Alkyl sulfonate + alkyl sulfonate
    Alkyl sulfonate + hydrocarbon (or additive)
    Fatty acid + organic phosphonic acid
    Amines + amines (hydrocarbons)
    Hydrocarbons + hydrocarbons
    Other: Hydroxamic acid + alkyl sulfonate (+ hydrocarbon), organophosphine
    Acid + organic phosphonic acid, alkyl sulfuric acid + alkyl sulfuric acid, etc.
    35
    15
    26
    20
    4
    4
    5
    9
    3
    15
    4
    8
    23.6
    10.1
    17.6
    13.5
    2.7
    2.7
    3.4
    6.1
    2.0
    10.1
    2.7
    5.4
    Note: Although the chelation reagent is very selective, it is expensive. It can only be used as an auxiliary collector for some non-ferrous metal oxide ore and rare metal ore. Since the formation of the integrator, the true metal bonding type is only Can be divided into "basic ionic" and "the covalent type", so in the statistical table, such collectors are temporarily used as a special category of non-ferrous metal oxides. This type of chelating agent is currently not a series of flotation products. [next]
    Table 4   Yellow medicine and black medicine combination flotation Pengxian copper mine results

    Pharmacy
    Pharmacy cost
    /yuan·t -1
    Raw ore grade
    /%
    Copper concentrate grade
    /%
    Recovery rate
    /%
    copper
    Zinc
    copper
    Zinc
    copper
    Zinc
    Butyl xanthate
    Nylonine black medicine
    Butyl xanthate + butyl ammonium black medicine
    (2:1)
    Butyl xanthate + butyl ammonium black medicine
    (1:1)
    13.7
    9.58
    8.90
    8.25
    0.76
    0.75
    0.77
    0.74
    1.16
    1.06
    1.14
    1.02
    14.31
    14.51
    18.46
    20.21
    3.45
    2.96
    2.16
    2.34
    88.71
    90.86
    91.67
    92.43
    14.98
    13.54
    14.17
    13.74

    Table 5   Benzyl phthalic acid, mixed toluic acid, styrenephosphonic acid and oxidized paraffin soap
    (fixed 0.9k g ·t -1 ) mixed test results of selected black pits

    Collector name
    Collector dosage
    / kg·t -1
    Concentrate /%
    Tailings grade
    /%
    Raw ore grade
    /%
    Sorting indicator
    /%
    Yield
    grade
    Recovery rate
    Benzyl phthalic acid
    Mixed toluene
    Styrene phosphonic acid
    0.2
    11.34
    10.02
    8.87
    30.30
    33.99
    37.65
    97.49
    95.71
    95.56
    0.10
    0.17
    0.17
    3.520
    3.595
    3.494
    86.15
    85.69
    86.69
    Benzyl phthalic acid
    Mixed toluene
    Styrene phosphonic acid
    0.15
    10.61
    10.06
    9.29
    32.37
    33.24
    36.60
    96.24
    94.41
    94.19
    0.15
    0.22
    0.21
    3.57
    3.54
    3.26
    85.63
    84.35
    84.88
    Benzyl phthalic acid
    Mixed toluene
    Styrene phosphonic acid
    0.10
    10.00
    9.97
    9.03
    30.84
    31.08
    34.57
    96.62
    95.83
    89.33
    0.12
    0.15
    0.41
    3.14
    3.277
    3.495
    86.62
    85.86
    80.30
    Benzyl phthalic acid
    8.87
    30.21
    89.96
    0.33
    3.000
    81.09
    Table 6   Tal oil fatty acid alone and its ether with sulfate
    Flotation of phosphate rock results when combined

    Pharmacy type
    Dosage /g·t -1
    Concentrate
    /%BPL
    Concentrate insolubles/%
    Tailings
    /%BPL
    Tailings insolubles /%
    Recovery rate
    /%BPL
    Tar oil
    fatty acid
    Tar oil fatty acid
    Ether sulfate
    (2:1)
    136
    273
    408
    544
    136
    273
    408
    544
    35.40
    41.52
    40.86
    36.27
    55.06
    53.97
    52.88
    53.53
    49.56
    42.99
    43.71
    49.66
    23.65
    25.09
    26.99
    25.20
    13.93
    6.56
    3.28
    1.97
    7.05
    3.06
    2.40
    1.75
    79.50
    90.15
    94.55
    94.66
    86.54
    94.55
    95.86
    96.39
    10.56
    64.84
    34.36
    90.28
    57.34
    83.00
    89.02
    92.29



    Figure 8-4-1 pH=6.5(1) and 9.5(2) and 6. 2(3) using octadecylamine as a collector,
    Effect of the amount of fat (a), phenol and polyethylene (b) and ether alcohol (c) on the flotation of hornblende

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