AU2009275989A1 - Reverse osmosis water treatment process that includes a decarbonation of a concentrate and a remineralization of a filtrate - Google Patents
Reverse osmosis water treatment process that includes a decarbonation of a concentrate and a remineralization of a filtrate Download PDFInfo
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- AU2009275989A1 AU2009275989A1 AU2009275989A AU2009275989A AU2009275989A1 AU 2009275989 A1 AU2009275989 A1 AU 2009275989A1 AU 2009275989 A AU2009275989 A AU 2009275989A AU 2009275989 A AU2009275989 A AU 2009275989A AU 2009275989 A1 AU2009275989 A1 AU 2009275989A1
- Authority
- AU
- Australia
- Prior art keywords
- water
- treatment process
- concentrate
- process according
- decarbonation
- Prior art date
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- Abandoned
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 110
- 238000000034 method Methods 0.000 title claims description 52
- 239000012141 concentrate Substances 0.000 title claims description 48
- 230000008569 process Effects 0.000 title claims description 36
- 238000001223 reverse osmosis Methods 0.000 title claims description 27
- 239000000706 filtrate Substances 0.000 title description 3
- 150000003839 salts Chemical group 0.000 claims description 30
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 18
- 239000013535 sea water Substances 0.000 claims description 18
- 239000006228 supernatant Substances 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000000395 remineralizing effect Effects 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 8
- 239000004571 lime Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 description 37
- 235000002639 sodium chloride Nutrition 0.000 description 31
- 238000010612 desalination reaction Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 235000019738 Limestone Nutrition 0.000 description 8
- 239000006028 limestone Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 238000009434 installation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 235000010216 calcium carbonate Nutrition 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- -1 bicarbonates Chemical class 0.000 description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical class [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 235000011160 magnesium carbonates Nutrition 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/06—Specific process operations in the permeate stream
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
- C02F5/06—Softening water by precipitation of the hardness using calcium compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
Description
REVERSE OSMOSIS WATER TREATMENT PROCESS THAT INCLUDES A DECARBONATION OF A CONCENTRATE AND A REMINERALIZATION OF A FILTRATE Field of the invention The field of the invention is that of water treatment. More precisely, the invention relates to the treatment of water, particularly seawater, for the purpose of the desalination thereof. 5 Prior art The desalination of seawater is a practice currently implemented for the purpose of lowering the concentration of various salts dissolved in the water. 10 To that end, it is known to filter salt-rich water through reverse osmosis-type membranes. This type of reverse osmosis filtration can be applied to any type of water containing salts, such as seawater. This type of reverse osmosis treatment proves to 15 be particularly effective in that it enables the production of purified water (or a filtrate) the salt concentration of which is considerably reduced. This is 2 clearly apparent in the columns of Table 1, which shows the results of treating seawater by reverse osmosis, with a conversion rate equal to 52.8%. In reverse osmosis or nanofiltration, the conversion rate can be 5 defined as being equal to the ratio (in %) between the permeate flux rate and the feed rate of the filtration unit. Parameters Seawater Desalinated Concentrate water (reverse osmosis Cations (mg/l) Ca 444.4 0.15 840.1 Mg 1382.7 0.47 2616.3 Ba" 1.10 0.1 1.9 Na" 12221.5 19 . 6 23056.6 K 416.1 0.85 784.3 Sr* 4.94 0.1 9.34 Anions (mg /l1) C- 21754 32.10 41046.02 SO 2963.2 0.40 5610.26
HCO
3 168.4 0.38 311.29 COz 3.5 0.000 9.49 NO3 1.0 0.00 1.87 Boron 5.4 0.35 9.06 F 1.5 0.02 2.80 3 Table 1: results of treating seawater by reverse osmosis with a conversion rate of 52.8%. It can indeed be observed that the concentrations of various salts initially present in the seawater are 5 considerably reduced in the desalinated water obtained after treatment by reverse osmosis. Depending on the species in question, these concentrations can reach values close to zero. However, although very effective, desalination by 10 reverse osmosis is not devoid of disadvantages. Disadvantages of the prior art In particular, the desalination of water by reverse osmosis is not a selective treatment in that 15 the water produced is depleted of numerous salts. However, although the desalination of water does indeed aim to reduce the salt concentration of the water, it more particularly aims to reduce the concentrations of certain salts so as to soften the water. In particular, 20 the desalination of water aims to limit the sodium chloride concentration of the water so as to eliminate the salty seawater taste thereof and to render same suitable for consumption, or more simply to render same usable. 25 Tn other words, the treated water derived from the desalination process is depleted of certain salts such as bicarbonates, whereas the presence thereof proves to be necessary. In order to mitigate this disadvantage, it is 30 common practice to remineralize treated water with a 4 view to enriching same with certain salts. Several techniques have been developed for this purpose. A first remineralization technique consists in injecting carbon dioxide (C02) and lime (CaO) into the 5 treated water, which results in the formation of calcium bicarbonates (Ca(HCO 3
)
2 ) in the treated water. A second remineralization technique consists in passing the treated water over a calcareous material after having injected an acid therein. The calcareous 10 material used for this purpose, for example, can have characteristics such as those which appear in Table 2. In particular, it may be of land origin, or formed naturally by evaporation of sea salts on coastal sites. Parameters% CaCO3 280 MgO 14.5 Si02 0.3 A120 3 0.05 S04- 0.2 Fe 2 03 trace Metals mg/kg Arsenic 0.25 Cadmium < 0.25 Chromium < 2 Mercury < 0.02 Lead 0.25 Selenium 0.9 Physical characteristics Hardness (Mohs) 3 5 Table 2: Exemplary characteristics of a conventional calcareous material The injection of carbon dioxide (C0 2 ) and the flow 5 of water over a calcareous material is accompanied by the following reaction: CaCO 3 + CO 2 + H 2 0 -* Ca (HC3) 2 10 The injection of sulfuric acid (H 2
SO
4 )and the flow of water over a calcareous material is accompanied by the following reaction: 2CaCO 3 + H 2
SO
4 -- Ca(HCO3)2 + CaSO 4 15 The injection of hydrochloric acid (HCl) and the flow of water over a calcareous material is accompanied by the following reaction: 20 2CaCO 3 + 2HC1 -* Ca(HC0 3
)
2 + CaCl 2 These remineralizataion techniques are particularly effective in that they enable the treated water to be enriched with calcium and bicarbonates. 25 However, they have a few disadvantages. Among these disadvantages is the fact that the calcareous material used according to the second technique for remineralizing treated water is consumed during the remineralization reaction. In this sense, it 30 comprises a consumable material which must be 6 continuously replenished. This requires the site on which the water is treated to be regularly supplied with this consumable material. This constraint has significant repercussions of a 5 logistic and economic nature in particular. Besides the aspects related to the supply of consumables, the desalination of water by reverse osmosis is accompanied by the production and discharge of concentrates into a natural environment. 10 When derived from the implementation of both the first technique and the second technique, these concentrates have very high concentrations of salts initially present in the water being treated. This appears in the right-hand column of Table I in which 15 the concentrations of the various salts present in these concentrates appear. In particular, it can be observed that these concentrates are particularly rich in calcium and magnesium ions and in bicarbonates. Due to the high salt concentrations of these 20 concentrates, the rejection of same into the natural environment is not impact neutral, but can, however, have a considerable impact on the environment. In particular, during desalination of seawater, these concentrates are discarded into the sea. This 25 brings about a sudden localized change in the salinity of the water. Such being the case, it has been observed that, even though certain animal or plant species are not affected by these sudden modifications in their environment, others are particular sensitive to same. 30 Objectives of the invention 7 In particular, the objective of the invention is to mitigate these disadvantages of the prior art. More precisely, one objective of the invention is to provide a water desalination technique which 5 includes a phase for remineralizing the treated water, the implementation of which results in limiting the supplies of consumables required for the remineralization process. The invention likewise pursues the objective of 10 enabling a particularly effective remineralization of desalinated water. Another objective of the invention is to implement such a desalination technique the implementation of which has only a limited impact on the environment, at 15 the very least in comparison with the techniques of the prior art. The invention also has the objective of providing such a technique which is simple to implement and which is effective and economical. 20 Disclosure of the invention These objectives as well as others, which will become apparent hereinbelow, are achieved by a process for treating water containing at least calcium and/or 25 magnesium salts through reverse osmosis-type membranes, said process comprising at least one step for collecting at least partially desalinated water, a step for collecting a concentrate coming from said membranes and containing bicarbonates, a step for injecting CO 2 30 or an acid into said at least partially desalinated water, and a step for remineralizing said at least 8 partially desalinated water in a remineralization reactor, characterized in that said process includes: - a step for decarbonating said concentrate so as 5 to form carbonates, and - a step for recycling at least some of said carbonates in said remineralization reactor. The invention is based on the implementation of a step for decarbonating the concentrate derived from the 10 reverse osmosis treatment, for the purpose of producing carbonates. These carbonates are then recycled inside the remineralization reactor in which they react with the treated water into which CO 2 or acid has been previously injected so as to enrich the treated water 15 with bicarbonates. Implementation of the invention consists therefore in directly producing on the water treatment site the calcareous material required for remineralization of the treated water. Therefore, implementing a water 20 treatment process according to the invention makes it possible to avoid continuously supplying the production site with a consumable calcareous material. In addition, the fact of subjecting the concentrate derived from the reverse osmosis water 25 treatment to decarbonation results in the discharge of a bicarbonate-depleted supernatant into the natural environment. This aspect of the invention therefore makes it possible to reduce the environmental impact of the desalination process. 30 According to one advantageous characteristic, said water consists of seawater.
9 Implementation of the invention enables seawater to be effectively desalinated and remineralized so as to render same suitable for consumption, or more generally to render same usable. 5 Said decarbonation step is preferably of the catalytic type. Catalytic decarbonation is a process which makes it possible to effectively form carbonates from the concentrate derived from reverse osmosis of the water 10 being treated. In this case, said carbonates formed are preferably in the form of balls. Catalytic decarbonation actually enables the formation of carbonate balls encasing a grain of sand. 15 These balls have the advantage of being easily reusable as a particularly effective remineralizing material. According to one advantageous aspect of the invention, said carbonates formed include calcium carbonate (CaCO 3 ). 20 Their use as a remineralizing material therefore enables the demineralized water to be calcium-enriched. According to another advantageous aspect of the invention, said carbonates formed include magnesium carbonate (MgCO 3 ). 25 Their use as a remineralizing material therefore enables the demineralized water to be magnesium enriched. It is of course possible to anticipate for different carbonates to be produced, so as to enrich 30 the treated water with other mineral species. According to the invention, said decarbonation 10 step is preferably preceded by a step for injecting soda or lime into said concentrate. These reactants actively participate in the formation of the carbonates. 5 Said lime or said soda is preferably injected in stoichiometric amounts with respect to the amount of bicarbonates to be precipitated, with a margin of 20 to 50%. Preferably, said CO 2 or said acid is injected in 10 stoichiometric amounts with respect to the amount of carbonates to be formed, with a margin of 20 to 50%. Such proportions enable good results to be obtained in terms of carbonate formation and in terms of lowering the salt concentration of the supernatant 15 which is rejected into the natural environment. A treatment process according to the invention advantageously includes a step for rejecting a supernatant coming from said decarbonation step into the natural environment, said supernatant being salt 20 depleted. Implementation of the invention therefore makes it possible to limit the environmental impact of water desalination. 25 List of the figures Other characteristics and advantages of the invention will become more apparent from the following description of a preferred embodiment, which is given for purely non-limiting and illustrative purposes, and 30 from the appended drawings, in which: - figure 1 is a schematic representation of an 11 embodiment of a installation intended for implementing a water treatment process according to the invention; - figure 2 shows an installation implemented when conducting tests carried out as part of the development 5 of the present technique. Description of an embodiment of the invention Reiteration of the principle of the invention The general principle of the invention relates to 10 a process for desalinating water by reverse osmosis, which includes a step for remineralizing the resulting desalinated water in a reactor. The invention is based on the implementation of a step for decarbonating the concentrate derived from the 15 reverse osmosis treatment for the purpose of producing carbonates. These carbonates are then recycled inside the remineralization reactor in which they react with the treated water into which C02 or acid has been previously injected so as to enrich the treated water 20 with bicarbonates. Implementation of the invention therefore consists in directly producing on the water treatment site the calcareous material required for remineralization of the treated water. Therefore, implementing a water 25 treatment process according to the invention makes it possible to avoid continuously supplying the production site with a consumable calcareous material. In addition, the fact of subjecting the concentrate derived from the reverse osmosis water 30 treatment to decarbonation results in the rejection of a bicarbonate-depleted supernatant into the natural 12 environment. This aspect of the invention therefore makes it possible to reduce the environmental impact of the desalination process. 5 Exemplary embodiment of an installation for implementing a water treatment process according to the invention In relation with figure 1, an installation is introduced, which is intended for implementing a water 10 treatment process according to the invention. As shown in this figure 1, such an installation includes means for feeding 10 salt-rich water, such as a pipeline, into a reverse osmosis filtration unit 11. This reverse osmosis treatment unit 11 is 15 connected to means for discharging 12 treated water which is at least partially salt-depleted, i.e., of which the salt concentrations that it initially contained are reduced. These discharge means 12 can assume the form of pipeline elements. 20 The means for discharging treated water 12 have an outlet which discharges into a remineralization reactor 13, which is itself connected to a pipeline for discharging 14 remineralized desalinated water. Reactant--injecting means 15, such as injectors, 25 are placed on the treated water discharge means 12 upstream from the remineralization reactor 13. The treatment unit 11 is likewise connected to means for discharging 16 a concentrate derived from the reverse osmosis treatment of the water being treated. 30 These means for discharging 16 a concentrate, which can assume the form of pipeline elements, have an 13 outlet which discharges into a decarbonation reactor 17. Reactant-injecting means 18 are placed on the means for discharging 16 the concentrate upstream from the decarbonation reactor 17. 5 The decarbonation reactor 17 has means for discharging 19 a supernatant. It further has means for discharging carbonates 20. These means for discharging carbonates 20 have an outlet which is connected to the remineralization reactor 13. 10 Example of a water treatment process according to the invention with a view to calcium enrichment of the desalinated water A water treatment process according to the 15 invention, for example, can be implemented in order to enrich desalinated water with calcium. Water which is rich in salts, in particular calcium, e.g., such as seawater or any other type of water, is conveyed towards and injected into the 20 reverse osmosis treatment unit 11 via pipeline 10. The salt-rich water is then filtered within this unit 11 so that treated water which is at least partially depleted of certain salts is extracted from the unit 11 and flows through the pipeline 12 in the 25 direction of the remineralization reactor 13. Before the water is injected into the remineralization reactor 13, the injected means 15 are implemented so as to inject therein carbon dioxide (C0 2 ) or an acid, e.g., such as sulfuric acid (H 2
SO
4 ) or 30 hydrochloric acid (HCl).
14 The concentrate derived from the reverse osmosis treatment of the salt-rich water is discharged from unit 11 by means of pipeline 16. This concentrate is particularly rich in calcium bicarbonates (Ca(HCO 3 )2). 5 Injection means 18 are implemented so as to inject lime (CaO) or soda (NaOH) into this concentrate. The mixture of the concentrate and lime or soda is then poured into the decarbonation reactor 17 for the purpose of undergoing a preferably catalytic type of 10 decarbonation. The principle of decarbonation is known by those skilled in the art. In this case, in particular, the catalytic decarbonation process developed and marketed by the applicant under the name of ACTINAO may be 15 implemented. Either of the following reactions then occurs within the decarbonation reactor, depending on whether lime or soda has been injected into the concentrate: 20 Ca(OH) 2 + Ca 2 + + 2HCO3 -> 2CaCO 3 4 + 2H 2 0 NaOH + Ca2 + 2HCO3 -- CaCO3: + H 2 0 + Na+ + HCO3 It can thus be observed that decarbonation of the concentrate results in the production of calcium 25 carbonates (CaCO 3 ) . The calcium carbonates thus produced constitute a calcareous material which is advantageously in the form of balls. A supernatant produced during decarbonation of the concentrate is discharged from the decarbonation 30 reactor 17 into the natural environment, via pipeline 19. Compared to the concentrate, this supernatant is 15 bicarbonate-depleted, such that the discharge thereof into the natural environment has less impact than that of direct disposal of the concentrate, as is the case in the techniques of the prior art. 5 The calcium carbonates produced during decarbonation of the concentrate are directed towards the remineralization reactor 13 with a view to being injected therein by means of pipeline 20. One of the following reactions then occurs within 10 the remineralization reactor 13, depending on the type of reactant previously injected into the treated water. The injection of carbon dioxide (C02) into the water produces the following reaction: 15 CaCO 3 + C02 + H 2 0 -4 Ca (HCO3) 2 The injection of sulfuric acid (H2SO4) into the water produces the following reaction: 20 2CaCO 3 + H 2
SO
4 -> Ca(HCO 3
)
2 + CaSO 4 The injection of hydrochloric acid (HC1) into the water produces the following reaction: 25 2CaCO 3 + 2HC1 -> Ca (HC03) 2 + CaCl 2 Within the scope of this embodiment, implementation of the invention therefore enables the desalinated water to be calcium enriched, while at the 30 same time preventing the purchase and supply of consumable calcareous material, insofar as the latter 16 is produced directly at the production site by recycling and reprocessing the residues derived from desalination of the water. 5 Example of a water treatment process according to the invention with a view to magnesium enrichment of the desalinated water In the same way as just described, a water treatment process according to the invention, for 10 example, can be implemented for the purpose of enriching desalinated water with magnesium. To accomplish this, water which is rich in salts, particularly magnesium, e.g., such as seawater or any other type of water, is conveyed towards and injected 15 into the reverse osmosis treatment unit 11 via pipeline 10. The salt-rich water is then filtered within this unit 11 so that treated water which is at least partially depleted of certain salts is extracted from 20 the unit 11 and flows through the pipeline 12 in the direction of the remineralization reactor 13. Before the water is injected into the remineralization reactor 13, the injected means 15 are implemented so as to inject therein carbon dioxide (C0 2 ) 25 or an acid, e.g., such as sulfuric acid (H 2
SO
4 ) or hydrochloric acid (HCl). The concentrate derived from the reverse osmosis treatment of the salt-rich water is discharged from unit 11 by means of pipeline 16. This concentrate is 30 particularly rich in magnesium (Mg (HCO3) 2 ) Injection means 18 are implemented so as to inject 17 lime (CaO) or soda (NaOH) into this concentrate. The mixture of the concentrate and lime or soda is then poured into the decarbonation reactor 17 for the purpose of undergoing a preferably catalytic type of 5 decarbonation. Either of the following reactions then occurs within the decarbonation reactor, depending on whether lime or soda has been injected into the concentrate: 10 Mg (OH) 2 + Mg 2 + + 2HCO3 -- 2MgCO 3 4 + 2H 2 0 NaOH + Mg2+ + 2HC03 - MgCO 3 4 + H 2 0 + Na+ + HCO 3 It can thus be observed that decarbonation of the concentrate results in the production of magnesium 15 carbonates (MgCO 3 ) . The magnesium carbonates thus produced constitute a calcareous material which is advantageously in the form of balls. A supernatant produced during decarbonation of the concentrate is discharged from the decarbonation 20 reactor 17 into the natural environment, via pipeline 19. Compared to the concentrate, this supernatant is bicarbonate-depleted, such that the discharge thereof into the natural environment has less impact than that of direct disposal of the concentrate, as is the case 25 in the techniques of the prior art. The magnesium carbonates produced during decarbonation of the concentrate are directed towards the remineralization reactor 13 with a view to being injected therein by means of pipeline 20. 30 One of the following reactions then occurs within the remineralization reactor 13, depending on the type 18 of reactant previously injected into the treated water. The injection of carbon dioxide (C0 2 ) into the water produces the following reaction: 5 MgCO 3 + Co 2 + H 2 0 -> Mg (HC 3 ) 2 The injection of sulfuric acid (H 2
SO
4 ) into the water produces the following reaction: 10 2MgCO 3 + H 2
SO
4 -> Mg (HCO3) 2 + MgSO 4 The injection of hydrochloric acid (HCl) into the water produces the following reaction: 15 2MgCO 3 + 2HCl -> Mg (HCO3)2 + MgCl 2 Within the scope of this embodiment, implementation of the invention therefore enables the desalinated water to be magnesium enriched, while at 20 the same time preventing the purchase and supply of consumable calcareous material, insofar as the latter is produced directly at the production site by recycling and reprocessing the residues derived from desalination of the water. 25 Tests Several series of tests were conducted so as to verify the effectiveness of a water treatment process according to the invention, and, in particular, so as 30 to compare the results of remineralization by means of conventional calcareous materials and by means of balls 19 of calcareous material produced by implementing the invention. The experimental protocol adopted during these tests is described with reference to figure 2, which 5 shows an installation implemented for this purpose. A first series of tests consisted in circulating an upward flow F of a sulfuric acid solution in a hollow cylindrical column 21 having a diameter of 3 cm and containing a bed of calcareous material 22, which 10 was previously washed in order to eliminate the fine particles therefrom, resting on a sintered glass support 23. The sulfuric acid solution used had a concentration equal to 200 mg/L and flowed at a rate of 15 6 ml/min. The bed of calcareous material 22 had a height of 24 cm, i.e., a volume of 170 cm 3 . Three types of calcareous material were alternatively used: Israeli limestone, Pyrenean limestone, and balls of calcareous 20 material produced by implementing the treatment process according to the invention. For each of the alternatively used calcareous materials, 300 ml of solution were sampled after an operating time of 1 hour and 30 minutes, for the 25 purpose of taking various measurements. A second. series of tests was carried out. These tests were identical to those carried out as part of the first series, except for the fact that the sulfuric acid solution used contained 1% seawater. 30 The results of the measurements taken as part of these first and second series of tests are listed in 20 Tables 3 and 4, respectively. TESTS No. 1 (without any addition of seawater) Israeli Pyrenean Balls limestone limestone Temperature T (OC) 20.3 20.3 20C .3 Conductivity (pS/cm) 545 499 880 PH 7.34 7.26 74-2 Alkali strength TA 0 0 0 Total alkali 18.0 12.5 15.1 strength TAC "F Degree of hardness 26.8 25.2 42.7 THca OF Total hardness 29.5 27.7 51.1 THtotal OF THMg (by difference) 2.7 2.5 8.4 Table 3: results of the first series of tests 5 TESTS No. 2 (with addition of seawater) Israeli Pyrenean Balls limestone limestone Temperature T(GC) 19.7 19.7 19.7 Conductivity (pS/cm) 1158 1196 1770 PH 7.35 7.34 7.64 Alkali strength TA 0 0 0 Total alkali strength 13.0 13.5 17.0 TAC F Degree of hardness 30.7 32.2 49.3 21 THca "F Total hardness 37.1 38.1 65.0 THtotal OF THMg (by difference) 6.4 5.9 15.7 Table 4: results of the second series of tests These tests make it possible to demonstrate the fact that the remineralization is more significant when 5 using balls obtained by implementing a process according to the invention than by using Israeli limestone or Pyrenean limestone. As a matter of fact, it appears that the total hardness (THTotal) of the solution sampled as part of 10 the first series, after treatment with balls of calcareous material, was of the order of 50'F, whereas it was less than 30*F after treatment with a conventional calcareous material. In the same way, it appears that the total 15 hardness (THTotal) of the solution sampled as part of the second series of tests, after treatment with balls of calcareous material, was of the order of 65'F, whereas it was lower than 40'F after treatment with a conventional calcareous material. 20 It can likewise be observed that remineralization is more significant in the presence of seawater. In conclusion, it can be noted that the balls of calcareous material obtained by implementing a process according to the invention have a high remineralizing 25 capability than a conventional calcareous material. Advantages 22 The implementation of a process according to the invention obtains numerous advantages. In particular, the invention enables desalinated water to be produced directly on the production site. 5 Implementing the invention therefore results in preventing the purchase of such a consumable and the continuous supplying of same, which has a direct positive impact on the cost of operating water desalination systems. 10 Furthermore, the calcareous material produced on site is obtained by treating and recycling the concentrate, i.e., by reusing the concentrate derived from desalination of the water by reverse osmosis. This calcareous material is therefore produced at a lower 15 cost due to the fact that it is produced from residues from the desalination of salt water directly available on site. It is likewise noted that the remineralizing capability of the calcareous material obtained by 20 implementing the invention is greater than that of a conventional calcareous material. This invention thus also has the advantage of enabling a more effective remineralization of desalinated water than the techniques of the prior art. 25 In addition, reprocessing of these concentrates results in the rejection into the natural environment of a supernatant which is carbonate-depleted and which therefore has lower salt concentrations than those of the concentrate itself. In other words, the rejection 30 of same into the natural environment has a less significant impact than the rejection of the salt-rich 23 concentrates produced according to the techniques of the prior art.
Claims (10)
1. Process for treating water containing at least calcium and/or magnesium salts through reverse osmosis membranes, which process includes at least one step for collecting water that is at least partially desalinated, 5 a step for collecting a concentrate coming from said membranes and containing bicarbonates, a step for injecting C02 or an acid into said at least partially desalinated water, and a step for remineralizing said at least partially desalinated water in a 10 remineralization reactor, characterized in that said process includes: - a step for decarbonating said concentrate so as to form carbonates, and - a step for recycling at least some of said 15 carbonates in said remineralization reactor.
2. Treatment process according to claim 1, characterized in that said water is seawater.
3. Treatment process according to either one of claims 1 or 2, characterized in that said decarbonation 20 step is of the catalytic type. 25
4. Treatment process according to any one of claims 1 to 3, characterized in that said carbonates formed are in the form of balls.
5. Treatment process according to any one of 5 claims 1 to 4, characterized in that said carbonates formed include calcium carbonate (CaCO 3 ).
6. Treatment process according to any one of claims 1 to 4, characterized in that said carbonates formed include magnesium carbonate (MgCO 3 ). 10
7. Treatment process according to any one of claims 1 to 7, characterized in that said decarbonation step is preceded by a step of injecting soda or lime into said concentrate.
8. Treatment process according to claim 7, 15 characterized in that said lime or said soda is injected in stoichiometric amounts with respect to the amount of bicarbonate to be precipitated with a margin of 20 to 50%.
9. Treatment process according to any one of 20 claims 1 to 8, characterized in that said CO 2 or said acid are injected in stoichiometric proportions with respect to the amount of carbonate to be formed with a margin of 20 to 50%.
10. Treatment process according to any one of 25 claims 1 to 9, characterized in that it includes a step of rejecting, in a natural environment, a supernatant resulting from said decarbonation step, which supernatant is salt-depleted.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0855309 | 2008-07-31 | ||
| FR0855309A FR2934584B1 (en) | 2008-07-31 | 2008-07-31 | PROCESS FOR TREATING WATER BY REVERSE OSMOSIS INCLUDING DECARBONATION OF A CONCENTRATE AND REMINERALIZATION OF A FILTRAT |
| PCT/EP2009/059676 WO2010012691A1 (en) | 2008-07-31 | 2009-07-27 | Reverse osmosis water treatment process that includes a decarbonation of a concentrate and a remineralization of a filtrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2009275989A1 true AU2009275989A1 (en) | 2010-02-04 |
Family
ID=40347842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2009275989A Abandoned AU2009275989A1 (en) | 2008-07-31 | 2009-07-27 | Reverse osmosis water treatment process that includes a decarbonation of a concentrate and a remineralization of a filtrate |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2310327B1 (en) |
| AU (1) | AU2009275989A1 (en) |
| ES (1) | ES2398882T3 (en) |
| FR (1) | FR2934584B1 (en) |
| IL (1) | IL210718A (en) |
| MA (1) | MA32584B1 (en) |
| WO (1) | WO2010012691A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2013214263B2 (en) * | 2012-02-03 | 2015-11-12 | Omya International Ag | Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use |
| AU2012301003B2 (en) * | 2011-08-31 | 2016-05-05 | Omya International Ag | Remineralization of desalinated and of fresh water by dosing of a calcium carbonate solution in soft water |
| WO2020212980A1 (en) * | 2019-04-17 | 2020-10-22 | Hutchison Water Israel E.P.C Ltd | A system and method for treating water |
| WO2025010402A1 (en) * | 2023-07-06 | 2025-01-09 | IDE Americas, Inc. | Sustainable desalination plant and sustainable method for the desalination of water |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL2418177T3 (en) * | 2010-08-13 | 2015-05-29 | Omya Int Ag | Micronized CaCO3 slurry injection system for the remineralization of desalinated and fresh water |
| IL212746A (en) * | 2011-05-05 | 2017-10-31 | David Sherzer | Water desalination system |
| ES2537376T3 (en) * | 2011-07-22 | 2015-06-08 | Omya International Ag | Injection system of a micronized CaCO3 suspension for remineralization of desalinated and fresh water |
| ZA201400203B (en) * | 2011-07-22 | 2015-04-29 | Omya Int Ag | Micronized caco3 slurry injection system for the remineralization of desalinated and fresh water |
| EA024001B1 (en) | 2011-09-07 | 2016-08-31 | Юнилевер Н.В. | Water purification system |
| LT2623466T (en) | 2012-02-03 | 2017-09-25 | Omya International Ag | Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use |
| ES2525646B1 (en) * | 2012-02-22 | 2015-11-10 | Abengoa Water, S.L. | FLUID REMINERALIZATION PROCEDURE |
| GB2499992B (en) * | 2012-03-05 | 2014-12-10 | Ide Technologies Ltd | Water mineralization |
| NO2695661T3 (en) | 2012-08-08 | 2018-03-03 | ||
| EP2805923B1 (en) * | 2013-05-24 | 2018-10-31 | Omya International AG | Installation for the preparation of a solution of calcium hydrogen carbonate suitable for the remineralization of water |
| EP2805924B1 (en) | 2013-05-24 | 2018-02-21 | Omya International AG | Multiple batch system for the preparation of a solution of calcium hydrogen carbonate suitable for the remineralization of desalinated water and of naturally soft water |
| EP3202719A1 (en) * | 2016-02-05 | 2017-08-09 | Omya International AG | Installation for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate |
| NL2021733B1 (en) | 2018-09-28 | 2020-05-07 | Univ Twente | Method for the production of drinking water |
| CN114275870A (en) * | 2021-12-29 | 2022-04-05 | 山东省水利科学研究院 | A method and device for remineralizing desalinated water by utilizing limestone slurry |
| ES2989227B2 (en) * | 2023-05-10 | 2025-09-02 | Acciona Agua S A | INSTALLATION AND PROCEDURE FOR WATER REMINERALIZATION |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2186963C (en) * | 1996-10-01 | 1999-03-30 | Riad A. Al-Samadi | High water recovery membrane purification process |
| IL137102A0 (en) * | 2000-06-29 | 2001-06-14 | Israel Garden | A process and apparatus for brine reformation |
| WO2006022719A1 (en) * | 2004-08-17 | 2006-03-02 | Anthony Pipes | Method and apparatus for parallel desalting |
| JP4773911B2 (en) * | 2006-08-14 | 2011-09-14 | 三菱重工業株式会社 | Drinking water production apparatus and method for producing drinking water |
-
2008
- 2008-07-31 FR FR0855309A patent/FR2934584B1/en not_active Expired - Fee Related
-
2009
- 2009-07-27 EP EP09781136A patent/EP2310327B1/en not_active Not-in-force
- 2009-07-27 WO PCT/EP2009/059676 patent/WO2010012691A1/en not_active Ceased
- 2009-07-27 ES ES09781136T patent/ES2398882T3/en active Active
- 2009-07-27 AU AU2009275989A patent/AU2009275989A1/en not_active Abandoned
-
2011
- 2011-01-18 IL IL210718A patent/IL210718A/en not_active IP Right Cessation
- 2011-02-22 MA MA33642A patent/MA32584B1/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2012301003B2 (en) * | 2011-08-31 | 2016-05-05 | Omya International Ag | Remineralization of desalinated and of fresh water by dosing of a calcium carbonate solution in soft water |
| AU2013214263B2 (en) * | 2012-02-03 | 2015-11-12 | Omya International Ag | Process for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate and its use |
| WO2020212980A1 (en) * | 2019-04-17 | 2020-10-22 | Hutchison Water Israel E.P.C Ltd | A system and method for treating water |
| WO2025010402A1 (en) * | 2023-07-06 | 2025-01-09 | IDE Americas, Inc. | Sustainable desalination plant and sustainable method for the desalination of water |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2934584A1 (en) | 2010-02-05 |
| ES2398882T3 (en) | 2013-03-22 |
| FR2934584B1 (en) | 2010-09-17 |
| IL210718A (en) | 2014-04-30 |
| EP2310327B1 (en) | 2012-11-07 |
| EP2310327A1 (en) | 2011-04-20 |
| WO2010012691A1 (en) | 2010-02-04 |
| IL210718A0 (en) | 2011-03-31 |
| MA32584B1 (en) | 2011-08-01 |
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