• 专利附录
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    • 专利摘要:
    Process for treating saline aqueous streams, in particular saline effluents, by membrane distillation with previous treatments, to eliminate total calcium hardness and permanent calcium hardness and the presence of sulfates in saline effluents, more particularly in residual brines from desalination plants. The system allows brines to be concentrated above 37% by weight, that is, above saturation, which makes it possible to considerably reduce the volume of the brine, adapt it for other industrial uses and produce pure water. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2548952A1
    申请号:ES201430584
    申请日:2014-04-21
    公开日:2015-10-21
    发明作者:Mohamed Khayet Souhaimi；María Del Carmen GARCÍA PAYO；Hicham EL BAKOURI；Abel RIAZA FRUTOS；Francisco Javier Bernaola Echevarria
    申请人:Abengoa Water SL；
    IPC主号:
    专利说明:

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    By "temporary calcium hardness" or "calcium carbonate hardness" is meant the presence of carbonic species in the aqueous stream to be treated that can react with calcium in order to form calcium carbonate.
    By "permanent calcium hardness" or "hardness of non-carbonates" is meant the presence of anions that can react with calcium to form more soluble salts at high temperature, that is, at a temperature that can be between about 50 ° C and about 80 ° C. This hardness is mainly due to sulfates and chlorides.
    By "total calcium hardness" is meant the hardness due to all calcium that can react with any anion to form calcium salts.
    In a preferred embodiment the temperature of stage (a) is essentially the same as the temperature of stage (c). By "essentially" it is understood in the present invention that said temperature may differ in a range between  1 ° C and 5 ° C, without varying the effectiveness and performance of this preferred embodiment of the process of the invention.
    In another preferred embodiment of the process of the invention, the temperature of step (a) is between 18 ° C and 85 ° C, more preferably between 25 ° C to 75 ° C. More preferably, step (a) is carried out under atmospheric pressure (approximately 1 atm.).
    The chemical treatment of step (a) of the process of the present invention will depend on the salts dissolved in the aqueous saline stream to be treated and the concentration thereof.
    In a more preferred embodiment of the present invention, the treatment of step (a) consists of the addition of sodium hydroxide, sodium carbonate or both in the aqueous salt stream for the removal of temporary and permanent calcium hardness, that is, for the removal of calcium that can react with the carbonic species of the aqueous saline stream to form calcium carbonate (CaCO3) plus calcium that can react with sulfates to form gypsum.
    When in the treatment of step (a) sodium hydroxide and sodium carbonate (NaOH) are added
    + Na2CO3) to the aqueous saline stream for the elimination of temporary and permanent calcium hardness, the reactions that take place are the following:
    image4 salt composition of the aqueous saline stream, the amount of reagents needed can be estimated as follows: - Carbonic acid neutralization: NaOH = {H2CO3-}
    - Calcium carbonate hardness: NaOH = {HCO3-} + {CO32-}
    - Calcium hardness of non-carbonates: Na2CO3 = {Ca2 +} - 2 {HCO3 -} - {H2CO3-} - {CO32-}
    To simplify the calculations, all concentrations ({}) are expressed in mg / L of CaCO3.
    In a preferred embodiment, the stoichiometric amount of NaOH necessary to neutralize the acid from the water and to remove the calcium hardness of carbonates as well as to eliminate the calcium hardness of non-carbonates is used to remove the temporary hardness.
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    Separation can be carried out by any technique known to a person skilled in the art such as decantation and / or by filtration systems, but not limited to these techniques.
    After step (b) of separation of the precipitated salts in step (a), step (c) is carried out, that is, the concentration of the aqueous stream obtained in said separation by membrane distillation at a temperature by below the boiling point of said aqueous stream and where the membrane is a hydrophobic and porous polymeric membrane, preferably microporous.
    In another preferred embodiment, the process of the invention further comprises step (d) of purification of the aqueous stream obtained in step (c) by membrane distillation at a temperature below the boiling point of said aqueous stream to be purified, and where the membrane is a hydrophobic and porous polymeric membrane, preferably microporous.
    The temperature at which membrane distillation is carried out, both in stage (c) or (d), is limited in its lower range by the temperature at which the treatment of stage (a) is carried out. .
    In another more preferred embodiment, the temperature of stage (d) is essentially the same as the temperature of stage (a) and more preferably the temperature of stages (c) and (d) are essentially the same as the temperature of the stage (a). By "essentially" it is understood in the present invention that said temperature may differ in a range between  1 ° C and 5 ° C, without varying the effectiveness and performance of this preferred embodiment of the process of the invention.
    In another preferred embodiment of the process of the invention, the temperature of stage (c) and / or stage (d) is between 18 ° C and 85 ° C, more preferably between 25 ° C and 75 ° C.
    The techniques or configurations of the concentration process by membrane distillation (DM) proposed in this invention can be selected from: membrane distillation with direct contact (DMCD), membrane distillation with scanning gas (DMGB), membrane distillation with air chamber (DMCA), membrane distillation with vacuum (DMV), membrane distillation with thermostated scanning gas (DMGBT), membrane distillation with liquid chamber (DMCL), and extends to any other mixed DM configuration.
    By "classic configuration" of DM we mean DM with Direct Contact, DM with Gas Scan, DM with Air Chamber or DM with Vacuum.
    By "mixed configurations" is meant in the present invention the combination of different classical DM configurations in the same module, for example thermostatic scanning gas (DMGBT) (a variant of scanning gas and air chamber); Liquid chamber (a variant of membrane distillation with air chamber and membrane distillation with direct contact); Direct and empty contact (DMCDV) by applying vacuum on the permeate side, or Low pressure sweeping gas (DMGBV) using a vacuum pump or a water tube in the sweeping gas. These mixed configurations are aimed at decreasing the vapor pressure on the permeate side in order to increase the driving force of the DM process.
    For example, the DMGBT system consists of a modification of the membrane distillation with scanning gas (DMGB) in which the air that sweeps the permeate side is thermostated inside the module by placing a metal plate through which the refrigerant (liquid or gas). In this way, the temperature of the permeate side is kept more constant and close to 25 ° C. Thus, the driving force of the process is achieved, that is, the
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    During the tests no suspended solids were seen in the food circuit, which were appreciated when the brine was used with NaOH + Na2CO3 treatment without heating (TQ1). The result obtained is shown in Table 2.
    The initial permeate flow through MEM1 has been of the order of 52.33 kg / m2h. The membrane permeability decreases with the operating time to values of the order of 17.53 kg / m2h after 14 hours of operation. At the end of the test a brine concentration of the order of 353.9 g / L was reached. Permeate electrical conductivity values remained below 300 μS / cm for the first 12 hours.
    In the tests carried out with membrane 2 (MEM2) a slight decrease in permeate flow of 74.34 kg / m2h, up to 56.14 kg / m2h after 6 hours of operation is observed. The feed concentration increased from 65.55 g / L to values greater than 324 g / L. The normalized concentration factor (β10) of the treated brine is 8.26. Regarding the electrical conductivity of the permeate, it is observed that the values remain below 500 μS / cm during the first 5 hours.
    The results of the tests carried out show the importance of treatment with soda and sodium carbonate at high temperature. This result confirms that the room temperature treatment does not completely eliminate CaCO3 or the calcium and carbonate ions present in the brine.
    Example 1.3. Procedure with the DMCD system using MEM1 and TQ3 membrane (Chemical treatment 3) as chemical treatment
    In TQ3, 1.9 g / L of Na2CO3 was added at a temperature of 75 ° C, during a reaction time of 15-30 min under stirring. A precipitate formed which was separated with prior decantation filtration.
    The stream separated from the precipitate was passed to the DMCD system under the following conditions (Tª of the food of 75ºC and Tª of the permeate of 25ºC). It is important to remember that the working temperature used in all technical feasibility tests of the membrane distillation process is 75 ° C for the food. The feed flow rate was 37.5 ± 2.5 L / h and the permeate was 32.5 ± 2.5 L / h. The result obtained is shown in Table 2.
    The tests performed using membrane 1 (MEM1) showed a decrease in permeate flow through the membrane over the operating time (59.68 kg / m2h versus 23.01 kg / m2h after 9 hours of operation ). With this treatment the brine can be concentrated from 62.06 g / L to 278.30 g / L, obtaining a normalized concentration factor (β10) of 4.96. However, the electrical conductivity of the permeate increased rapidly after 8 hours, denoting a deterioration of the membrane characteristics.
    Example 1.4. Procedure with the DMCD system using MEM1 and TQ4 membrane (Chemical treatment 4) as chemical treatment.
    The results with the previous treatments seem to indicate that the crystalline phase that most influences the brine concentration process is calcium sulfate and, therefore, it would be necessary to apply procedures in order to previously eliminate this crystalline phase.
    Sulfate content can be reduced by providing excess calcium to form the plaster and / or adding barium salts. The example indicated below, tries to show the advantages of the treatment of brine with barium salts since this procedure is very effective and allows an almost total elimination of sulfates. The test shown was performed with Membrane 1 to compare the results of the different chemical treatments.
    image10
    Similarly, small variations in the initial electrical conductivity of the brine have been observed. Therefore, in order to better compare the different treatments, a normalized electrical conductivity Ωn has been defined as:
    Ω treated brine (t)
    Ωn (t) = Ω (t = 0)
    Comparing the different treatments used in DMCD for MEM1 and MEM2 membranes in terms of the normalized permeate flow and the normalized electrical conductivity of the food, it can be concluded that for an aqueous salt current with characteristics "similar" to those presented in this invention The most effective chemical treatment for MEM1 is TQ4, that is, brine treated with BaCl2. By "similar" is meant in the present invention saline effluents from desalination plants, containing a concentration of TDS greater than 40 g / L with an electrical conductivity greater than 60 mS / cm. With the brine treated with BaCl2, the highest normalized concentration factor, β10, of 7.62 is obtained, with the reduction in permeate flow being less significant (less than 20%). It should be mentioned that in brine from desalination plants, the concentration of SO42- ions is much higher than the concentration of carbonic species, so it can be concluded that the most effective treatment is one that allows a removal of calcium hardness permanent. The TQ2 treatment (with NaOH and Na2CO3 at 75 ° C) is a suitable treatment since the brine was concentrated above the maximum concentration that allows a water solution (353.9 g / L for MEM1) but at a lower flow than that obtained with TQ4, which can influence the process time.
    With the TQ1 treatment the results for the MEM1 membrane are very similar to those obtained with the TQ2 treatment. For the MEM2 membrane it can be concluded that the TQ2 treatment proved to be quite effective.
    EXAMPLE 2.- Estimation of the useful life of MEM1
    It is based on the same current as for example 1, that is, an aqueous saline stream of saline effluents from desalination plants, containing 66.7 ± 2.7 g / L of total dissolved solids (TDS), with a electrical conductivity of 74.7 ± 1.8 mS / cm at 25 ° C. Table 1 shows the main salts contained in the salt stream used in these examples.
    A DMCD test was performed with the MEM1 membrane and brine treated with BaCl2 (TQ4 described in example 1.4.) To estimate the life of the membrane. It is based on a treated aqueous saline stream, which contains 65 ± 3 g / L of total dissolved solids (TDS) and an electrical conductivity of 74.8 ± 1.8 mS / cm at 25 ° C. To estimate the useful life, the replacement of the permeate volume in each one hour measurement is considered and the feed tank is filled with treated brine, at the concentration of 65 g / L, that is, less than the concentration of the brine retained in the feed. The idea is to evaluate whether it is possible to have a DMCD system running continuously with the brines of a desalination plant. It has been observed that the life of the membrane is lengthened producing constant permeate flows. In FIG. 1 permeate flows are observed as a function of operating time. Dashed lines represent measurement days.
    As shown in Fig. 1 the permeate flow starts with 51.33 kg / m2h and descends progressively for approximately 24 hours, at which point it becomes more or less constant at around 30 kg / m2h.
    The feed concentration amounts from 66.8 ± 3.2 g / L TDS to 277.0 ± 3.2 g / L TDS during the 72 effective hours considered for the test. Note that the value of the feed concentration at 72 hours exceeds the saturation concentration of the
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    By increasing the salinity of the food, the permeate flow is reduced and the vapor inlet pressure in the membrane pores is exceeded, which significantly reduces the process performance and impairs the quality of the permeate.
    Example 3.3. Procedure using membrane distillation with thermostated scanning gas (DMGBT) and TQ5 as chemical treatment.
    Starting from the same aqueous stream described for the previous examples and for TQ5, 0.4 g / L of NaOH and 1.9 g / L of Na2CO3 were added at a temperature of 75 ° C, during a reaction time of 15-30 min under stirring. A precipitate formed which was separated with prior decantation filtration. Then, 9.7 g / L of BaCl2 was added at room temperature, during a reaction time of 20-40 min under stirring. A precipitate formed which was separated with prior decantation filtration.
    It is based on an aqueous salt stream treated with TQ5, which contains 56.2 ± 2.2 g / L of total dissolved solids (TDS) and an electrical conductivity of 67.1 ± 1.4 mS / cm at 25 ° C. The stream separated from the precipitate was passed to the DMGBT system under the following conditions (Tª of the food of 75ºC and Tª of the metal plate of the permeate side of 25ºC). The flow of the feed flow is 100 L / h while the air flow remains constant at 25.1 ± 1 L / min, which means speeds within the membrane module of 0.07 and 1.10 m / s for food and air, respectively.
    Throughout the test, the permeate flow is more or less stable, decreasing only 15.21% with respect to the initial value (35.46 kg / m2h). This can be explained by the absence of solutes that tend to precipitate throughout the brine concentration process, decreasing the "fouling" of the brine.
    The food concentration increases from 56.2 g / L TDS to 275.13 g / L in 9.5 hours of operation, with the β10 value being 5.15. The electrical conductivity of the permeate is maintained at acceptable values.
    Table 3 also shows a comparison of the results obtained with membrane distillation systems (DMGBT and DMCA) with the same treatments described above and without treatment. The indicators considered are the permeate flow, the maximum TDS concentration reached in the supply current, the maximum electrical conductivity, the concentration factor and the normalized concentration factor, β10.
    The conditions under which DMCA experiments are carried out are similar to those performed in DMGBT. The flow of the feed flow was 100 L / h. The temperature of the food was 75 ° C and the temperature of the metal plate where the vapors are condensed inside the module was 25 ° C.
    In the DMGBT and DMCA experiments without treatment, the same aqueous saline stream described in Example 1 is used.
    Table 3: Summary of values obtained for the different tests with DMCA, DMGBT.
    MEM1 MEM2 membrane
    Chemical treatment DMCA Without TQDMGBT Without TQDMGBT TQ2DMGBT Without TQDMGBT TQ2DMGBT TQ4DMGBT TQ5
    Permeate flow 24.2228.6431.3526.1331.0029.9333.86
    medium (kg / m2h)
    Maximum Caliment (TDS, g / L) 175.5163.6296.03158.90250.3261.98275.13
     maximum food (mS / cm) 146.2139.6199.0136.9181.5186.2191.3
    β 2.872.804.662.133.763.774.89
    β10 (in 10 h) 2.613.114.242.663.763.775.15
    Test time (h) eleven9eleven810109.5
    5
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    35
    In relation to the results obtained in the DMGBT configuration with different treatments, it can be said that the treatment with NaOH and Na2CO3 at 75 ° C in the DMGBT configuration is more effective than the test without treatment. As can be seen in Table 3, the best results correspond to the DMGBT configuration with treatment, being able to concentrate the brine to values greater than 296 g / L for the MEM1 membrane and 250 g / L for the MEM2 membrane.
    To make a better comparison of the results, the normalized permeate flows and the normalized electrical conductivity of the food for the different membranes in the DMGBT configuration with and without treatment (without TQ) have been calculated. In view of the normalized values it can be concluded that for the DMGBT configuration using MEM2 the best treatment is TQ5, that is, with NaOH + Na2CO3 + BaCl2. However, for the type of current from which we start, it may not be necessary to use NaOH to obtain these results if the conclusions drawn in the DMCD configuration are taken into account.
    In the case of MEM1 a slight improvement is observed with the TQ2 treatment with respect to the untreated brine. The permeate flow normalized with the treated brine is greater and remains practically constant for longer than that of the untreated brine.
    EXAMPLE 4-. Combined hybrid system: chemical treatment + DMCD + DMGBT
    Below is a proposal for a combined hybrid system for the concentration and purification of brines from desalination plants with the aim of achieving “zero discharge”. A configuration of this combined hybrid system consists of a brine treatment plus a conventional membrane distillation system (eg DMCD) and a mixed one (eg DMGBT). Depending on the characteristics of the water to be treated, the most appropriate treatment procedure can be chosen. This system is also not limited to the use of flat membranes (MEM1 and MEM2), other types of porous and hydrophobic membranes of different structures, hollow fibers, etc. can be used. In no case is it limited to any temperature range, being able to operate at different pH values. Finally, it is not limited to the use of brines from reverse osmosis plants.
    In this more preferred configuration, DMGBT, the working conditions are essentially the same as in the previous examples in DMGBT. By "essentially" it is understood in the present invention that temperatures may differ in a range between  10 ° C (permeate) and 25 ° C (feed) and the flow rate of the feed flow may differ by  100 L / h while the flow of air may differ by  25 L / min.
    In this more preferred configuration, DMCD, the working conditions are essentially the same as in the previous examples in DMCD. By "essentially" it is understood in the present invention that temperatures may differ in a range of between  10 ° C (permeate) and 25 ° C (feed) and the flow rate of the feed and permeate flow may differ in a range of between  25 L / h and 200 L / h.
    In this example, the operating parameters of the proposed new system are presented (FIG. 3):
    The brine or saline effluent (12) is subjected to one of the chemical treatments described in the present invention (13), using as reagents: sodium hydroxide NaOH, sodium carbonate Na2CO3, calcium hydroxide Ca (OH) 2, calcium chloride CaCl2, Barium chloride BaCl2 or any other necessary chemical reagent or combinations thereof, depending on the starting effluent (12). The salts formed in the treatment (14) (essentially salts such as: calcium carbonate CaCO3, barium carbonate BaCO3, strontium carbonate SrCO3, magnesium carbonate MgCO3, calcium and magnesium mixed carbonate CaxMg1-xCO3, calcium phosphate Ca3 (PO4) 2, calcium fluoride CaF2, magnesium hydroxide Mg (OH) 2, calcium sulfate CaSO4 in different degrees of hydration, and silica) are separated by filtration and / or decantation.
    Subsequently, the salt stream circulates through a simple or "classic" membrane distillation system (15), for example DMCD, DMGB, DMCA or DMV, using a hydrophobic and microporous membrane with a pore size of less than 250 nm (such as the MEM1 of the previous examples, which allows to achieve higher concentrations and has an acceptable shelf life). When the concentration of the food exceeds the saturation concentration of the limiting salt (CR> CS), the brine passes through a crystallizer (17) in which the salts capable of forming are recovered. From the remaining effluent with salts of high solubility (18) salts of high added value can be recovered. During this thermal concentration process, product water (21) is obtained which can be mixed with the permeate of the first DM passage.
    Since the quality of the permeate (19) decreases over time, it has been proposed to treat the permeate of the first DM passage with a mixed membrane distillation configuration
    (16) (eg DMGBT or DMCL)) with a microporous hydrophobic membrane with a pore size greater than 250 nm as with, for example, MEM2 of the previous examples. In this way, water of a high quality (20) (electrical conductivity of less than 5 μS / cm at 25 ° C) and a concentrate (22) can be obtained that can be used in the reaction chamber (13) or in the first step of the DM (15).
    When the concentration of the retention (CR) in the system (16), such as DMGBT, is close to 50-60% of the saturation concentration (CS), it can be recirculated to the system (15), such as DMCD. With this mixed configuration, a "zero discharge" would be achieved.
    权利要求:
    Claims (1)
    [1]
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