• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A novel method of reducing metal impurities in aqueous metal halide solutions, especially alkaline earth metal ions. and a novel organic solvent composition having a synergistic activity for removal of metal impurities form aqueous solutions. Said solvent composition contains an effective amount of at least one complexing agent of the group consisting of 1-aryl-3-methyl-4-acyl-pyrazol-5-one wherein the acyl is derived from an organic carboxylic acid of 1 to 18 carbon atoms and a thenoyl-substituted keto compound and a complexing additive selected from the group consisting of trialkylphosphine oxides and trialkylphosphates.
    公开号:SU1215615A3
    申请号:SU792777003
    申请日:1979-06-01
    公开日:1986-02-28
    发明作者:Мария Спазьянте Пласидо；Джуффре Луиджи；Кастольди Альдо；Сиоли Джанкарло
    申请人:Оронцио Де Нора Импианти Элеттрохимичи С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to the purification of solutions of sodium chloride from impurities, in particular from calcium ions and magnesium, for the use of purified solutions in membrane electrolyzers.
    A known method for purification of brines by two-stage liquid extraction with liquid, in which the brine is first contacted with an organic solvent phase containing a chelating agent, such as di 2-ethylhexane 1) phosphoric acid, and a second promoter, such as an alkyl phosphoric acid ester, phosphine oxide or alkanol, with obtaining a purified aqueous brine, and an organic phase containing impurities, which is then washed with an acid to remove impurities in the form of water-soluble salts, for example, in the form of calcium chloride, chlorine iron and magnesium chloride ij.
    However, the content of calcium and magnesium ions in brine remains in the order of 5 and 4 mg / l, respectively, which. too many for membrane electrolyzers, for which it is required that the content of calcium ions and mag1-sh is less than 0.5 mg / l, preferably less than 0.2 mg / l,
    The aim of the invention is to increase the degree of purification.
    This goal is achieved by the method of purifying sodium chloride solutions of calcium ions with magnesium by treating with a solution of a precipitating agent in an organic solvent which is not miscible with water and containing a complexing additive, as saline (its agent uses 1-Fensch1 3-methyl -4-benzoyl-pyrazol-5-one or thienoyl trifluoroacetone, and as a complexing agent trioctylphosphine oxide or tributyl phosphate and treatment of the initial solution are 0.00-0.0 with a 1 M precipitating agent solution containing 0.2-2 , 0 us, 7 complex Braz guide additives.
    In the quality of water-immiscible organic solvents, aromatic hydrocarbons such as toluene, xylo and benzene, oxygen-containing hydrocarbons such as cyclohexanone, alkanols such as ai alcohol, chlorinated hydrocarbons, carbon tetrachloride, and such
    1215615
    0
    five
    0
    five
    0
    five
    0
    five
    hydrocarbons, like kerosene, which is preferred because of its low cost and low toxicity. In addition, kerosene does not form emulsions with aqueous brines of alkali metal halides in a wide range of pH.
    The concentrations of the complexing agent can vary over a wide range up to the saturation concentration of the organic solvent. Preferably, the concentration is 0.001-0.01 M. The use of more dilute solutions requires a large number of extraction steps. Preferably, the use of a grating end of the complexing agent is 0.2-2.0% by weight.
    The compositions according to the proposed method are distinguished by a high complexing ability with respect to metal ions in aqueous alkaline alkali metal halide brines, which is superior to that when using individual components. The content of calcium and magnesium ions in brine containing 300–310 g / l of chloride can be reduced to a concentration of less than 0.2 mg / l, so low that it cannot be determined using sensitive analytical instruments,
    The synergistic effect was demonstrated in experiments with an organic complexing solution. additives, taken separately, which rightly did not affect the concentration of metal ions, were taken separately with an organic solution of the complex-forming agent, which also slightly reduced the concentration of metal ions, and the organic solution of the first and second , which differed in the values of shm-by-activity.
    Aqueous solutions of alkali metal halides should have an alkaline pH, preferably 10.5 to 12, before contact with an organic solvent. During the extraction steps, the pH is reduced until it becomes slightly acidic, so that higher pH is preferable. Starting with brine pH 11, the pH decreases to 6 after contact with the organic acid solution. Under these conditions x a compromise is reached between the stability of the calcium complexes formed
    3
    and magnesium and p are soluble in water chelating agent. At pH 6, the solubility in water of the chelating agent-E of its agent is insignificant and decreases at a more acidic pH.
    The alkalinity of the brine can be set up before each extraction step by adding a suitable base, such as an alkali metal hydroxide, for example sodium hydroxide.
    After the extraction step, the organic solution is treated with an aqueous solution of a strong acid, for example hydrochloric, which removes metallic impurities from it in the form of calcium chloride and magnesium chloride in the aqueous phase. The organic phase is then recycled for re-extraction. You can use other acids, such as sulfuric, nitric and phosphoric, whose magnesium and calcium salts are soluble in water.
    The volume ratio of an aqueous solution of an alkali metal halide and an organic solution can vary within wide limits depending on the type of contact between the two phases, the interrelationships of the phase densities and the duration of the contact. The indicated volume ratio may be 1: 1-10: 1, preferably 1: 1-5: 1. Contact between the two phases can be achieved, for example, by mechanical movement, centrifugation in the stuffed and dish-shaped columns. After the extraction stage, two phases can be separated, for example, by decanting and then extracting the organic phase with an aqueous acid solution, for example, by mechanical displacement, etc. The organic phase is then recovered to a brine extraction step, which may be a simple extraction or may consist of multiple cycles.
    In a preferred embodiment of the invention, the crude brine, which may contain a concentration of calcium ions 160, magnesium ions 100 and iron ions 10 mg / l, is first treated in accordance with the traditional method of flocculation, decantation and filtration to remove the number of metal ions, and then the brine is subjected to extraction by the proposed method
    five
    to reduce the content of calcium and magnesium ions to less than 0.2 mg / l, typically in a single extraction step.
    The following examples describe several preferred embodiments of the invention.
    Example I. A series of experiments on cleaning conducted with water brine,
    containing 300 g / l of sodium chloride, 13.5 mg / l of calcium ions and 10 mg / l of magnesium ions, and kerosene with additives was used as an organic extractant. The pH of brine was set in the range of 11.5-12 with sodium hydroxide solution before extraction, and the volume ratio of the organic phase to the aqueous was 1: 1-0.5: 1. Extraction was carried out with stirring
    at 25-30 ° C for 5 minutes and after each stage of extraction, the amount of calcium and magnesium ions in brine was determined.
    Then the organic phase was separated from the aqueous brine phase and stirred with an equal volume of 18% hydrochloric acid for 5 minutes to remove calcium and magnesium ions from it. Then the organic phase was decanted, ned, and used for the next extradition.
    The results are shown in Table 1, where TTL corresponds to thienoyl trifluoroacetone, the formula of which has the form
    ABOUT
    LT
    ABOUT
    II
    C-CHn-C-CF
    45
    PMBP corresponds to 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one, the formula of which is
    / L
    Ox 1 t
    50
    TOPO is trioctylphosphine oxide, and TBP is tributyl phosphate.
    The results of table 1 demonstrate 55 synergistic effect of the composition according to the proposed method. When using only complexing agent, even with relatively
    at a high concentration of 1.40 wt.%, the content of calcium and magnesium ions after 3 extractions decreases only to 3 and 0.5 mg / l, respectively, whereas after two extractions, with a complexing agent with a concentration of 0.023 wt.% and an additive. the concentration of magnesium and calcium ions (for both) decreases to below 0.2 mg / l, which is the limit of sensitivity of the analytical instruments used. When using a complexing agent with a concentration of 0.28 wt.% And an additive during one extraction, the content of calcium and magnesium ions is reduced to less than 0.2 mg / l.
    Example 2 Aqueous brine containing 300 g / l of sodium chloride, 185 mg / l of calcium ions and 50 mg / l of magnesium ions was extracted according to the method of example 1 with kerosene containing 0.28 wt.% PMBP and 2 wt.% TOPO. After one extraction, the content of calcium and magnesium ions was 3 and 2 mg / l, respectively. After the second extraction, the content of calcium and magnesium ions was below the sensitivity of the instruments (0.2 mg / l).
    Example 3. The experiments were carried out according to example 2 with the difference that the brine, in addition, contained 50 mg / l
    Tta
    0.5
    rm: № 0.05
    TORO TV
    ten
    15
    0
    five
    0
    five
    active chlorine to determine the stability of the complexing agent and additive in relation to the active chlorine present in the solution. After 30 extraction cycles, the ability of the kerosene mixture to extract calcium and magnesium ions remained unchanged.
    EXAMPLE 4: For a comparative analysis of the compositions according to the proposed and known methods. The following experiment was carried out. An aqueous brine containing 300 g / l of sodium chloride, 100 mg / l of calcium ions and 100 mg / l of magnesium ions, was extracted with a kerosene solution containing 0.28% by weight of PMBP and 2% by weight of TOPO and a kerosene solution containing 2 May , 7 di- (2-ethylhexyl) - phosphoric acid and 2 wt.% Of tributyl phosphate.
    The results are shown in table 2.
    From the results of table 2 it is obvious that the proposed method is superior in its results limestone.
    Thus, the invention makes it possible to increase the degree of purification of sodium chloride solutions to such an extent that it makes possible their use in membrane electrolyzers,.
    Table I
    85
    61
    4,50,5
    7.56
    41.2
    2,80,5
    13,110
    13,59,8
    1.15
    , 40

    Molar concentration
    Additive
    Additive concentration, may. %
    Ttl
    Tta
    RBBR
    Rwdr
    0.001
    TOGO
    0.2
    0.001
    0.001
    0.001
    Tv
    TORSO
    TVR
    0.2
    0.2
    0.2
    11.5 0.8 0.023
    ,, 2
    11.3 0.6 0.023
    ,, 2
    11.1 0.6 0.028
    ,, 2
    11.2 0.5 0.028
    , 2.0.2
    РМВР 0,01 SARS 2 1 0, 2 0,28
    TTA 0,01 SARS 2 ,, 2;. 0.23
    ... ". J-in-J-M.i. --- .- uj-L-ijI -" j-Lj-ii-i Lj ".- i-i. mfmmr - r fI- -n-- --1--
    Table2 Extracting substance Content, mg / l
    РМВР and ТОРО 0,2,2
    Di- (2-ethylheyl) phosphorus
    acid and tributyl phosphate And 19
    Compiled by N. Yarmolyuk Editor I. Rybchenko Tehred T. Tulik Proofreader V. But ha
    Order 915/62 Circulation 452Subscription
    VNII1Sh State Committee of the USSR
    for inventions and discoveries
    YZOZZ, Moscow, Zh-35, Raushsk nab. 4/5
    Branch PPP Patent, Uzhgorod, st. Project, 4
    1215615
    8 Continuation of table 1

    Content, mg / l
    Sa
    Md
    Concentration, May L
    0.2
    0.2
    0.2
    0.2
    权利要求:
    Claims (1)
    [1]
    METHOD FOR CLEANING SODIUM CHLORIDE SOLUTIONS from calcium and magnesium ions by treatment with a solution of a precipitating agent in a water-immiscible organic solvent containing a complexing additive, characterized in that, in order to increase the degree of purification, 1-phenyl-3-methyl4- is used as a precipitating agent benzoyl-pyrazol-5-one or thienoyltrifluoroacetone, and trioctylphosphine oxide or tributylphosphate as a complex-forming additive. the treatment of the initial ^ solution is carried out with a 0.001-0.01 M solution of a precipitating agent containing 0.2-2.0 wt.% complexing additives.
    1 12
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT24141/78A|IT1202862B|1978-06-02|1978-06-02|PROCESS FOR THE DEPURATION OF SALAMOIE|
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