Method And Facility For Treating Aqueouos Effluents From The Primary Circuit of A Nuclear Power Plant Comprising Boric Acid

Abstract

The present invention relates to a process for treating aqueous effluents from the primary circuit of a nuclear power plant implementing a separation of boric acid using a reverse osmosis membrane, characterized by the fact that it comprises steps consisting of treating the effluents using a multi-stage assembly composed of reverse osmosis modules comprising a membrane with a high boron rejection rate, arranged in parallel and in series, and recycling of the intermediate products to different points in the assembly.

Claims

1. A process for treating aqueous effluents comprising a separation step of boric acid from the aqueous effluents, the aqueous effluents coming from a primary circuit of a nuclear power plant, the process using a reverse osmosis membrane, wherein the process comprises steps consisting in treating the aqueous effluents using a multi-stage assembly composed of reverse osmosis modules, each reverse osmosis module comprising a reverse osmosis membrane with a high boron rejection rate, the reverse osmosis modules being arranged in parallel and in series, and the multi-stage assembly comprising recycling of the intermediate products at various points in the multi-stage assembly.

2. The process for treating aqueous effluents as claimed in claim 1, comprising a step of filtering boric acid by reverse osmosis so as to obtain a boric acid fluid having a boric acid concentration of the order of 7500 mg.sub.B/L at an outlet of a reverse osmosis module and to obtain a purified fluid having a boric acid concentration of the order of 5 mg.sub.B/L at an outlet of another reverse osmosis module.

3. The process for treating aqueous effluents as claimed in claim 1, wherein the aqueous effluents have a pH much lower than the pKa of boric acid.

4. The process for treating aqueous effluents as claimed in claim 1, wherein the boron rejection rate of the reverse osmosis membranes is greater than 80%, preferably greater than 90%.

5. The process for treating aqueous effluents as claimed in claim 1, wherein the reverse osmosis membranes are composed of a support, for example of polysulfone, covered with a dense film, the dense film providing selectivity toward boron, for example of polyamide or polyisobutylene.

6. The process for treating aqueous effluents as claimed in claim 1, wherein the reverse osmosis membranes are formed from an organic material, such as membranes based on asymmetric polymers or composite of polyamide type, polyimide, polysulfone, fluorinated polymer, silicone polymer, vinyl polymer, cellulosic polymer, inorganic material such as carbon molecular sieves, graphenes, zeolites, native or functionalized porous silica, in the form of homogeneous or heterogeneous structures, such as charged membranes, in particular with a dispersed phase of the nanoparticle type or functional polymers of the aquaporin type, or materials which have undergone a surface treatment to improve performance.

7. The process for treating aqueous effluents as claimed in claim 2, which implements a boric acid enrichment zone providing the boric acid fluid and a boric acid depletion zone providing the purified fluid, each of the boric acid enrichment zone and the boric acid depletion zone comprising several reverse osmosis modules and one or more stages in series, the process comprising a step of progressively increasing the boric acid concentration in the boric acid enrichment zone so as to reach a desired boric acid concentration, the process comprising a step of progressively reducing the boric acid concentration in the depletion zone so as to reach a required purified water concentration.

8. The process for treating aqueous effluents as claimed in claim 7, wherein each stage consists of a number of reverse osmosis modules arranged in parallel adapted so as to ensure a desired flow rate circulating at each stage.

9. The process for treating aqueous effluents as claimed in claim 7, wherein each reverse osmosis membrane lets through a permeate which is a liquid less concentrated in boric acid than an incoming liquid in the reverse osmosis membrane and retains a retentate which is a liquid more concentrated in boric acid than the incoming liquid, a permeate off each reverse osmosis module of the enrichment zone being recycled, the permeate being previously mixed with the aqueous effluents with an incoming fluid in another reverse osmosis module, with the boric acid fluid or with the purified fluid.

10. The process for treating aqueous effluents as claimed in claim 7, wherein each reverse osmosis membrane lets through a permeate which is a liquid less concentrated in boric acid than an incoming liquid in the reverse osmosis membrane and retains a retentate which is a liquid more concentrated in boric acid than the incoming liquid, a retentate of each reverse osmosis module of the depletion zone being recycled, the retentate being previously mixed with the aqueous effluents, with an incoming fluid in another reverse osmosis module, with the boric acid fluid or with the purified fluid.

11. The process for treating aqueous effluents as claimed in claim 7, wherein the retentates off the reverse osmosis modules of the enrichment zone are directly mixed with the boric acid fluid.

12. The process for treating aqueous effluents as claimed in claim 7, wherein the permeates of the reverse osmosis modules of the depletion zone are directly mixed with the purified water.

13. The process for treating aqueous effluents as claimed in claim 1, further comprising steps of measuring the boric acid concentration at selected points of the multi-stage assembly and, based on the result of the concentration measurements, performing a step of driving the reverse osmosis modules of the multi-stage assembly in order to optimize the boric acid concentration in the boric acid fluid.

14. The process for treating aqueous effluents as claimed in claim 13, wherein measuring the boric acid concentration is made at an inlet and outlets of the multi-stage assembly.

15. The process for treating aqueous effluents as claimed in claim 13, wherein measuring the boric acid concentration is made at intermediate points of the multi-stage assembly.

16. The process for treating aqueous effluents as claimed in claim 13, wherein measuring the boric acid concentration is made directly.

17. The process for treating aqueous effluents as claimed in claim 13, measuring the boric acid concentration is indirectly.

18. The process for treating aqueous effluents as claimed in claim 13, wherein measuring the boric acid concentration is made on-line.

19. The process for treating aqueous effluents as claimed in claim 13, measuring the boric acid concentration is made off-line based on a sample.

20. The process for treating aqueous effluents as claimed in claim 13, wherein the aqueous effluents are recycled back to the inlet of a reverse osmosis module when the process efficiency at the outlet is measured to be less than the treatment objectives.

21. A facility for treating aqueous effluents from a primary circuit of a nuclear power plant, the aqueous effluents comprising boric acid, by implementing a separation of boric acid as claimed in claim 1 by means of a reverse osmosis membrane, wherein the facility comprises a plurality of stages composed of reverse osmosis modules, each reverse osmosis module comprising a reverse osmosis membrane with a high boron rejection rate and means for recycling intermediate products to different points of the facility.

Description

DESCRIPTION OF THE FIGURES

[0063] Other features, purposes and advantages of the present invention will become apparent from the following detailed description and the accompanying drawings, which are given by way of non-limiting examples and wherein:

[0064] The previously described FIG. 1 schematically represents a facility in accordance with the state of the art for the separation of boric acid by means of a thermal process,

[0065] The previously described FIGS. 2 and 3 schematically represent a reverse osmosis module, in a spiral design for FIG. 3,

[0066] FIG. 4 illustrates the phenomenon of concentration polarization in the vicinity of a membrane,

[0067] FIGS. 5 and 6 represent two examples of facilities in accordance with the present invention comprising, respectively, a set of four enrichment stages and four depletion stages and a set of three enrichment stages and three depletion stages,

[0068] FIGS. 7A, 7B, and 7C and respectively 8A, 8B, and 8C represent simulations of boric acid concentration in retentates Cr, membrane Cw and permeate Cp for the figures associated with the index A, simulations of the flow rate to the permeates for the figures associated with the index B and simulations of the osmotic pressure for the figures associated with the index C as a function of the membrane surface area deployed over a stage for a water supply of 12 m.sup.3/h at a boric acid concentration of 50 mg.sub.B/L for FIG. 7 and respectively 1500 mg.sub.B/L for FIG. 8, and

[0069] FIGS. 9 and 10 represent two examples of management of the module feeds in the different stages as a function of flow rate and boric acid concentration.

DETAILED DESCRIPTION OF THE INVENTION

[0070] The incoming water, i.e., the effluent to be treated, is originally from intentional discharges of fluid from the primary water circuit and contains boric acid. The boric acid concentration fluctuates during the operation of the nuclear power plant, in a range comprised between 0 and 2000 mg.sub.B/L (expressed as mass of boron B per liter of effluent).

[0071] The objective of the invention is to jointly produce: [0072] concentrated boric acid, for example at 7500 mg.sub.B/L, [0073] purified water with low boric acid content, for example less than 5 mg.sub.B/L.

[0074] It is proposed to use membrane separation techniques instead of the thermal separation described in the prior art. The solution consists in combining new technological components that have been proven for other industrial applications.

[0075] In the proposed solution, the effluent is treated by a multi-stage process composed of reverse osmosis modules with a high boron rejection rate, arranged in parallel and in series, and recycling of intermediate products at different points of the process. The treatment allows the joint generation of concentrated boric acid and purified water, both potentially reusable in the nuclear power plant.

[0076] Both products can be reused in the nuclear reactor if the chemical specifications allow it, or can be transferred to an additional processing step.

[0077] In the invention, it is proposed to use reverse osmosis membranes with a high boron rejection rate, developed and used in the seawater desalination industry. These membranes have boron rejection rates of the order of 90%.

[0078] The boron rejection rate of the membrane R.sub.m is defined as:

[00001]$\begin{array}{cc}{R}_m=1-\frac{C_p}{C_m}& \left[\mathrm{Math}.1\right]\end{array}$

[0079] Where C.sub.p is the boron concentration on the permeate side of the membrane and C.sub.m is the boron concentration on the retentate side of the membrane surface.

[0080] FIG. 4 schematically illustrates the membrane 12 defining a retentate side 13 and a permeate side 14. The liquid on the retentate side 13 flows in the direction 20, and on the permeate side the liquid flows in the direction 22. A boundary layer 24 on the surface of the membrane defines a zone where the velocity distribution on the retentate side 13 is influenced by the presence of the membrane 12.

[0081] The membranes of interest for the invention are characterized by a boron rejection rate higher than conventional membranes, preferably higher than 80%. Current commercial membranes with high boron rejection rates are generally composite membranes consisting of a support (for example of polysulfone) covered with a dense film offering selectivity toward boron (for example of polyamide, polyisobutylene).

[0082] The described device is applicable to any type of material presenting a permselectivity (difference of speed of passage of water and boron in steady state), implemented in a membrane cascade for which the different stages are equipped with one or several permselective materials. The materials used can be organic (asymmetric polymeric membranes or composites such as polyamide, polyimide, polysulfone, fluorinated polymers, silicone polymers, vinyl polymers, cellulosic polymers, etc.), inorganic (carbonaceous molecular sieves, graphenes, zeolites, native or functionalized porous silica, etc.), of homogeneous or heterogeneous structures. The heterogeneous character includes charged membranes of the mixed-matrix membranes type (with a dispersed phase of the nanoparticles type or functional polymers of the aquaporins type, etc.) or materials having undergone a surface treatment to improve performance (fluorination, bromination, sulfonation or any type of functionalization, etc.).

[0083] The proposed process implements a multi-stage assembly or architecture of boron-selective reverse osmosis modules. Examples of such an architecture are represented in FIGS. 5 and 6.

[0084] FIG. 5 shows a process using a multi-stage assembly of four enrichment stages, four depletion stages, where the permeates in the enrichment zone and the retentates in the depletion zone are completely recycled to the process feed. Each enrichment and depletion stage generates intermediate products, corresponding to the two outputs—retentate and permeate—of each stage. At each stage of the enrichment zone, the intermediate product of primary interest is the retentate (since it is more concentrated in boric acid than the feed of said stage) and the intermediate product of secondary interest is the permeate (since it is more diluted in boric acid than the feed of said stage). Conversely, at each stage of the depletion zone, the intermediate product of primary interest is the permeate and the intermediate product of secondary interest is the retentate.

[0085] It is possible to create a total recycling of an intermediate product, i.e., to return the total flow of an intermediate product generated at one stage to the feed of a stage located further upstream. This is the case in the situation in FIG. 5 for intermediate products of secondary interest that are returned to the general process feed.

[0086] It is possible to create a partial recycling, i.e., to return part of the total flow of an intermediate product generated at one stage to the feed of a stage located further upstream. This is the case with connections 40e.4 and 40a.4.

[0087] It is possible to create a total or partial bypass, i.e., to send all or part of the total flow of an intermediate product generated at a stage to a process output. This is the case with connections 44, 44.1, 44.2, 44.3, 42, 42.1, 42.2 or 42.3.

[0088] FIG. 6 shows a process using a multi-stage assembly of three enrichment stages, three depletion stages, the permeates in the enrichment zone e are totally recycled to the process feed, the retentates in the depletion zone are recycled to the feed of the module preceding their output module. There are also partial recyclings to the feed (grey lines), and bypasses (40a.4). A finishing stage f is placed at the end of the enrichment zone, with recycling of the retentate from the stage to the feed of this same stage, allowing a transient treatment to be carried out through a finishing reverse osmosis stage 10f, circulating in a closed circuit on this tank, until the target boric acid concentration is obtained.

[0089] In general, there are different possible options for multi-stage architecture or assemblies, which are presented below and numbered from 1 to 9.

[0090] 1) the presence of an enrichment zone e and a depletion zone a, each composed of several membrane modules. The zones can for example be defined from the outlet of a first reverse osmosis module 10. The retentate output 13 is sent to the enrichment zone e, and the permeate output is sent to the depletion zone a. A feed module 32 and a pump 30 feed the effluent to be treated to the module 10.

[0091] 2) the enrichment zone is responsible for gradually increasing the boric acid concentration and is composed of one or more stages in series 10e.1, 10e.2, 10e.3, and 10e.4 to achieve the boric acid concentration specifications. Here, two modules are arranged in series where the retentate output of one module is sent to the input of the next module in the series.

[0092] 3) the depletion zone is responsible for gradually reducing the boric acid concentration and is composed of one or more stages in series 10a.1, 10a.2, 10a.3, and 10a.4 to achieve the purified water specifications. Here, two modules are arranged in series where the permeate output of one module is sent to the input of the next module in the series, optionally passing through a pump 30.1, 30.2, etc.

[0093] 4) each stage consists of one or more modules in parallel to handle the flow through each stage.

[0094] In FIGS. 5 and 6, only one reverse osmosis module is shown per stage, but there may be several modules arranged in parallel. An arrangement of three modules in parallel is shown in FIG. 10. The three inputs of modules 10.1, 10.2 and 10.3 are connected together to an input channel 200, as are the three retentate outputs connected together to a retentate channel 220 and the three permeate outputs connected together to a permeate channel 210. Such an arrangement has a single inlet 200, a retentate outlet 220, and a permeate outlet 210, similar to a single reverse osmosis module. Thus, it is possible to replace a single reverse osmosis module with an arrangement of three or more modules arranged in parallel.

[0095] 5) in the enrichment zone e, the permeate 14.e.1, 14.e.2, 14.e.3, etc., of each module can be recycled [0096] after mixing with the process feed (for example using the channel 34 in FIGS. 5 and 6); [0097] after mixing with the feed from another process module; [0098] to one of the process outputs;

[0099] 6) in the depletion zone a, the retentate 13.a.1, 13.a.2, 13.a.3, etc., of each module can be recycled [0100] after mixing with the process feed (for example using the channel 36 in FIGS. 5 and 6); [0101] after mixing with the feed from another process module (for example using the channels 38.1 and 38.2 in FIG. 6); [0102] to one of the process outputs;

[0103] 7) each process product, concentrated boric acid and purified water, can be partially recycled at any point in the process (for example using the channels 40e.4 and 40a.4 in FIGS. 5 and 6),

[0104] 8) the retentates from the modules in the enrichment zone can bypass the upstream series modules and directly reach the process outlet for the concentrated boric acid (for example using the channels 42, 42.1, 42.2 and 42.3 in FIGS. 5 and 6),

[0105] 9) the permeates from the modules in the enrichment zone can bypass the upstream modules in series to directly reach the process outlet corresponding to the purified water (for example by using the channels 44, 44.1, 44.2 and 44.3 in FIGS. 5 and 6),

[0106] The choice among these different possible options of architecture or multi-stage assembly from 1 to 6 makes it possible to meet the specifications of the process with respect to the target concentration in concentrated boric acid and in purified water. Features 7 to 9 allow the process to be controlled, so as to adapt the operating conditions according to the boric acid concentration at the process feed (fluctuating over time).

[0107] To ensure the passage of water through the membrane, the hydraulic pressure difference on both sides of the membrane must be greater than the osmotic pressure difference (dependent on the concentrations of boric acid and dissolved salts in solution) on both sides of the membrane.

[0108] The membrane surface area required for each stage is calculated in order to achieve the desired recovery rate knowing the flow rate to be treated and the applied transmembrane pressure.

[0109] The recovery rate is the ratio of the permeate flow rate of a stage to its feed rate.

[0110] FIGS. 7A, 7B, 7C, 8A, 8B and 8C show simulation results for an osmosis stage, using the following data (these are reference values determined from experimental laboratory measurements and correspond to an unfavorable design): water permeability 2.2.Math.10.sup.−12 m/Pa/s; rejection ratio 0.8; mass transfer coefficient 10.sup.−5 m/s (for calculation of the concentration bias). The curves correspond to a water feed of 12 m.sup.3/h with a boric acid concentration between 50 mg.sub.B/L (FIGS. 7A, 7B, 7C) and 1500 mg.sub.B/L (FIGS. 8A, 8B, 8C) for a transmembrane pressure difference of 40 bar (higher than the osmotic pressure difference).

[0111] Increasing the membrane surface area increases the permeate flow rate (and thus the recovery rate) and the retentate concentration. On the other hand, the permeate concentration also increases, as well as the osmotic pressure.

[0112] Once the characteristic parameters of the membrane are determined from experimental measurements (water permeability, rejection rate, mass transfer coefficient), this type of simulation makes it possible to choose the best conditions to reach the desired specifications.

[0113] The process is scaled up by choosing a multi-stage process architecture or assembly from the possibilities described above, and by defining the hydraulic pressures and the deployed membrane surfaces at each stage: [0114] The hydraulic pressures must be higher than 1 bar and lower than 80 bar, preferentially between 5 and 50 bar [0115] The recovery rate for each stage should preferentially be less than 90% [0116] The recycling rates, i.e., the fraction of the flow recycled to the feed, of each product can vary from 0 to 99%, preferentially from 0 to 50%

[0117] These choices must ensure the separation performance of the process whatever the boric acid concentration in the process feed. The operating conditions can be adapted over time in order to manage this temporal fluctuation.

[0118] The purpose of the process control is to measure the separation efficiency of the process, as well as to adapt the operating conditions in order to maintain the target concentrations of concentrated boric acid and purified water despite the variation of the boric acid concentration in the feed.

[0119] The separation efficiency of the system can be monitored by measuring (continuously or by spot sampling) the concentrations of substances of interest at different points of the process. The boric acid concentration can be measured at the inlet of the reverse osmosis system, as well as at the concentrated boric acid and purified water outlets. Intermediate measurements can also be used to complete this information. The boric acid concentration can be measured directly (for example by assay) or indirectly (for example via pH), on-line or off-line using a suitable sampling device.

[0120] On the one hand, the effect of fluctuating concentration at the process feed can be compensated for by managing the feed to the osmosis modules. Depending on the boric acid concentration at the process feed, the same stage will be fed with fluctuating flow rates and concentrations.

[0121] In general, the number of modules in parallel on the same stage should be increased when the flow rate is higher, in order to have more membrane surfaces. It is also advisable to increase the number of stages in series when the separation objectives are more difficult to achieve. This is particularly the case when the boric acid concentration is lower in the enrichment zone or higher in the depletion zone. FIG. 9 illustrates the situation of two reverse osmosis modules arranged in series, in two consecutive stages n and n+1. FIG. 10 illustrates the situation of three reverse osmosis modules arranged in parallel, in two consecutive stages n and n+1, with stage n+1 comprising no reverse osmosis module. The multi-stage architecture or assembly of FIG. 9 is more suitable than that of FIG. 10 when the flow rate to be treated is lower and the separation objectives are more difficult to achieve.

[0122] On the other hand, operating parameters can be adjusted, such as the recycling rates of each of the process products, as well as the operating pressures (via the use of feed pumps and adjustable valves).

[0123] Finally, if the measured efficiency is below the treatment objectives, all effluents can be recycled to the feed to increase the effluent throughput time in the process.

[0124] The advantages of the proposed solution over the processes concern: [0125] Compactness: membrane modules generally deploy exchange surfaces between phases of several thousand m.sup.2 per m.sup.3, compared with a few hundred for the linings and trays of thermal processes. In particular, thermal processes by evaporation require a height of the order of 10 meters, compared with about 2 meters for membrane processes. This aspect reduces the cost of civil engineering in particular. [0126] Energy expenditure: the process operates at a temperature close to room temperature and does not require vaporizing part of a liquid phase. The process consumes a few hundred kilowatts of electricity, compared with several megawatts of heat for evaporation. [0127] The modularity of the system, allowing easy adaptation of the design and operation. [0128] Flexibility, by dispensing with the hydrodynamic constraints (clogging, weeping) of thermal processes. [0129] Economic gains on the investment cost (smaller footprint, gas/liquid contactor made of plastic instead of steel) and operating costs on the utilities (no need for steam, less energy consuming).

[0130] In the context of the present invention, when values are indicated, they should be considered as giving an indicative value that may change within a range of the order of plus or minus 10% of the indicated value.

[0131] Of course, the present invention is not limited to the above-described embodiments but extends to any alternatives consistent with its spirit.