ES2380476B2 - TREATMENT PROCESS OF SALTED OR SALOBRE WATER THAT REDUCES THE SALINITY OF THE VEGETABLES TO MAKE THEM COMPATIBLE WITH THE RECEIVING ENVIRONMENT GETTING CHEMICAL PRODUCTS. - Google Patents

Abstract

Saltwater or brackish water treatment process that reduces the salinity of the spills to make them compatible with the receiving environment by obtaining chemical products. # The present invention has its application in the construction industry and installation of water treatment plants With high saline content, determining a physicochemical procedure to reduce the salinity of the spillage, in this process we get several commercial chemicals. # The treatment consists of several phases, according to figure 1. In phase 1 the initial water is treated with several reagents obtaining synthetic plaster and chlorine gas. In phase 1a we obtain magnesium hydroxide and in phase 2 we obtain synthetic gypsum and water with low salt content whose discharge can be made to some receiving medium or other uses. # It has a direct application in the reduction of salts from the rejection water from desalination plants.

Description

Saltwater or brackish water treatment process that reduces the salinity of the spills to make them compatible with the receiving environment, obtaining chemical products.

Object of the invention

The present invention has its application in the sector of the construction and installation industry of water treatment plants with high saline content (brackish), and determines a procedure to reduce the salinity of the discharge by means of a physicochemical process that makes it compatible with the receiving medium, while we get various chemicals.

Specifically, it has a direct application in the elimination of salts from rejection water from desalination plants.

Prior art

Given the water deficit in Spain and its growing needs, new systems for obtaining potable water are being developed, especially the seawater desalination technique.

In recent years, various salt or brackish water treatment technologies have been developed, leaving no solution to rejection water from desalination techniques.

Among the most advanced desalination or water treatment techniques that produce rejection water, we currently have electrodialysis, reverse osmosis, nano fi ltration, ultrafiltration, etc.

It is known that the production of rejection water in desalination by reverse osmosis is similar to the production of desalinated water generated, that is, for each m3 of water produced with desalination, 1 m3 of rejection water is generated.

From the updated data of the Spanish Ministry of Environment and Rural and Marine Environment, within the AGUA program, it follows that in the Mediterranean coast when all the plants are planned in service and at full capacity, more than 600 Hm3 / year of water will be obtained total desalted, an amount that is similar to the rejection water that will be poured into the sea, with a salt concentration much higher than the usual marine environment. This, carried out continuously, will cause serious damage to the environment along the coast with irreversible repercussions for the marine habitat.

Some techniques of elimination of this rejection water are being used, such as direct discharge to nearby rivers, waterways, artificial lakes, burial at great depths, drying salines, but none of them gives the appropriate solution that avoids contamination and the effect negative to the environment.

Currently, the dilution method has been generalized, which is a relative solution of great energy cost, and consists of mixing, in very high proportions, from 1 to 4 or 5 in volume, rejection water and seawater, subsequently injecting in the sea mixes with optimum inclination and adequate pressure to produce a good dilution, so that it affects the marine environment as little as possible. This technique pours the mixture at a distance close to the coast and since the amount of existing salts has not actually been reduced, the fl ora and marine fauna can be harmed.

It is a fact that among other living beings of the Mediterranean, there is the oceanic Posidonia phanerogam, which forms grasslands, creating one of the most important ecosystems in the ecology and economy of the Mediterranean coast. According to data from approved specialized research centers, approximately the surface of the Posidonia Oceanic prairies in the Mediterranean is approximately 4 million ha, the extent and density of the prairies depend on the physical and environmental characteristics of the environment where they are established .

It is good to highlight the ecological importance of the Posidonia Oceanic meadows, as they are the main oxygen producer of the sea, they can generate from 4 to 20 l / m2 / day, according to the sources already mentioned. The average oxygen production is 14 l / m2 / day. With these data, the average daily oxygen production in the Mediterranean Sea would be above half a million Hm3.

At present, the ecosystems formed by the Posidonia meadows have suffered a 50% regression with respect to the estimated data of 40-50 years ago. According to sources of studies of standardized centers, the average annual regression is between 3% and 5%, it means that in a decade we would reach a loss of 50% of the current surface, that is, we would lose 2 million ha of surface area. meadow in the case of maintaining the current conditions of contaminating affection to the marine environment.

The ideal conditions for the development of an oceanic Posidonia meadow are: clean, well-oxygenated waters, free of contaminants, with organic matter, adequate depth, and a temperature between 15 and 20ºC as optimal. It is considered that in order not to drastically affect the life of the Oceanic Posidonia, salinity should not exceed the usual saline threshold of seawater (38.5 g / l), at a value greater than 10% in salinity, it is In other words, the salinity value should not be exceeded by more than 3.85 g / l to guarantee the survival of the mentioned phanerogam, a figure that if the discharges of the rejection water of the desalination plants continue, together with another type of Discharged directly and continuously, the disappearance of these plants could occur in certain areas of the sea.

The existence of this plant, which grows near the seashore, can be jeopardized by the hypersalinity of the new discharges and the increase in temperature that will lead to produce less oxygen and a lower concentration of oxygen [O2] dissolved in the seawater will make the life of fish and other living beings that need it more difficult, and even the disappearance of marine life can be achieved if the oxygen concentration progressively decreases.

The Oceanic Posidonia will be greatly affected in the case of returning the rejection water directly to the sea, affecting its growth and even its life, which leads to a progressive decrease in the amount of oxygen produced by this plant, a protected Mediterranean endemic species by current legislation (Community Directive 97/62 / EEC of October 27, 1997; Royal Decree of December 7, 1995; Order of January 23, 1992 of the Generalitat of Valencia).

On the other hand, the Posidonia meadows have a great capacity to sequester atmospheric CO2, about 0.5 million tons / year, which makes them the most important CO2 sinks in the entire Mediterranean. Oceanic Posidonia not only absorbs CO2 when it is alive, as is the case with the other phanerogams, but also accumulates it by burying it in the sediments, and removes carbon from the circuit for thousands of years. The rest of these plants return the fixed CO2 a year or a year and a half. Therefore, the degradation that entails the loss of the biodiversity of these ecosystems would aggravate the problem of global warming, since their disappearance would generate a source of CO2 where there is now a sink.

The vulnerability of underwater grasslands to the supply of rejection water through submarine emissaries, which also increases the temperature of their normal habitat, as well as salinity and non-absorption of CO2, can lead to serious environmental damage to the marine ecosystem and atmosphere, consequently serious and irreversible for the inhabitants of the planet.

It has also been proven, in the coastal area, the existence of precipitate that is manifested in the milky white color set in the marine water near the beach. This repeated observation makes us think that it may be calcium sulfate dihydrate, which under certain conditions precipitates.

On the other hand, it is convenient to publicize the fact that in Spain there are numerous quarries for the exploitation of products that have a high content of calcium components that are taken to landfills because they are not useful for construction. This material can be useful to carry out our chemical treatment process that we develop in this patent.

We also inform the current situation of the Spanish chloroalkaline industry in relation to the harmful effects generated to the environment by the emission of mercury into the atmosphere. The concentration of this element in the air exceeds 19,000 ng / m3 in some plants that are currently in operation in Spain, being the limit established by the EPA (Environmental Protection Agency) of 300 ng / m3.

The system for obtaining chlorine in the producing industries installed in Spain is the electrolytic method, consisting of the application of an electric current to a certain ionic substance that allows its ions to be separated.

The most universally used industrial manufacturing process for chlorine is the electrolysis of a saline solution of sodium chloride (NaCl) or potassium chloride (KCl), called brine, by passing electrical energy through it. Chlorine (Cl2) and sodium hydroxide (NaOH), also called caustic soda, or potassium hydroxide (KOH), also called caustic potash, are also produced, also obtaining hydrogen gas (H2) as a co-product.

Electrolysis occurs in a cell where there are two compartments or electrodes: the positive pole or anode and the negative pole or cathode, so that when the electric current passes through the saline solution, the positive ions (Na + oK +) are attracted towards the opposite sign pole, the cathode, and the negative ions (Cl−) are attracted to the anode. Three different types of technology are currently applied: Electrolysis with mercury amalgam cell, electrolysis with membrane cell and electrolysis with diaphragm cell. Of these three technologies, the first one is currently used in 7 of the 9 plants installed in our country. What supposes a 78% of the annual production of 828 thousand tons, that is to say, 645 thousand tons of chlorine obtained through an obsolete technology that pollutes the environment due to the expulsion of mercury to the atmosphere.

From all of the above, the importance of treating salt or brackish water and giving a solution to the rejection water that is generated is deduced, eliminating the negative effects of its direct incorporation into the sea or the natural environment.

All this leads to a starting solution that is to directly use a salt or brackish water treatment process that minimizes salts and, therefore, the rejection that is generated is minimal. Consequently, we will generate, with this process, a lower environmental impact by producing less pollutants in the water and the atmosphere. And in addition, we get chemicals such as synthetic plaster that can be used in construction; chlorine, without expelling mercury into the atmosphere; and hydroxides, as well as a discharge compatible with the requirements of current regulations.

Description of the invention

It is a chemical process that is used to treat any type of salt or brackish water, reducing the salinity of the spill.

The present invention seeks to solve, in general, the problem posed in the current saltwater or brackish water treatment systems with rejection water, through an analytical and chemical process that minimizes spillage products.

This process is carried out in three distinct phases (Figure 1: process diagram).

First phase of this process: We want to eliminate all the chloride ions existing in the water to be treated (1) to eliminate this element of the process in order to continue reducing the salinity of the treated water, for this we add hydrogen peroxide (2) with a percentage by weight between 20 and 50%, and sulfuric acid (3) in adequate doses and concentration (normality between N / 10 and 5N), together with a metal oxide type catalyst (4) to increase the reaction rate and a secuestrene (5), which is capable of capturing the calcium and magnesium ions, and when the pH has been regulated at the optimum point of precipitation of the synthetic plaster, release the calcium ion, keeping the magnesium ion retained. By properly regulating the pH of the system between 5 and 7, we transform the existing chlorides to obtain chlorine gas (6), which would condense properly collecting in tanks, at the corresponding pressure and temperature for possible commercialization for domestic or industrial use (7 ).

The fi ltered water obtained is free of chlorides, corroborated by pertinent tests with silver nitrate, so that we would obtain water with soluble sulfates and synthetic plaster (8), due to the initial existence of calcium cations.

We would carry out a process of fi ltration of this water to separate the synthetic plaster by means of fi ltration through a physical process, such as the passage through a screen of suitable mesh light to retain the precipitate of synthetic plaster (9) and pass water without chlorides and with soluble sulfates (10).

Phase 1a of this process: after separating the chlorine gas obtained in phase 1, as well as the synthetic plaster in the case of the existence of calcium ions, and provided we have the water filtered without chlorides and with soluble sulfates with the presence magnesium ion (10), we proceed in this phase to the elimination of this ion, going directly to phase 3 if we did not have the presence of magnesium.

In this phase, we would add alkaline hydroxides (11) to the fi ltered water from the previous phase (10), in amounts suitable to transform magnesium into magnesium hydroxide (12). After a physical filtration process by decantation through a suitable mesh light screen, we would obtain magnesium hydroxide and water filtered with soluble magnesium-free sulfates (13).

It is demonstrable through chemical analysis the non-existence of magnesium ion, treating the water obtained with potassium ferrocyanide, which in the presence of ammonium ion would precipitate in the form of potassium and ammonium magnesium ferrocyanide, KNH4Mg [Fe (CN) 6].

Second phase of the process: we follow the treatment of the water filtered with soluble sulfates obtained in the previous phases (13), for this we add soluble calcium component free of chlorine (14) (selectable between calcium carbonate, quicklime, calcium bromide, iodide of calcium or calcium hydroxide) in appropriate doses and concentrations by properly regulating the pH between 5 and 7 with sulfuric acid (3) with a normal between N / 10 and 5N, we quantitatively transform all sulfates into synthetic gypsum that precipitates (9). We perform a process of fi ltering this water

(15) to separate the synthetic plaster by fi ltration through a physical process such as that performed in the first phase. Thus, after filtering, we obtain water with soluble alkaline hydroxides without sulfates (16) which can be used in phase 2 in the case of magnesium (19), or as hydroxide can be commercialized for industrial uses (17) or water discharge (18).

It is demonstrable through quantitative chemical analysis, the non-existence of sulfate and calcium in the fi nal fi ltered water, and that the precipitate obtained in the fi ltration of phases 1 and 3, corresponds exclusively to synthetic gypsum. This has been proven by taking said precipitate to special analyzes performed with an electron microscope in approved laboratories of different faculties and higher technical schools, whose reports are attached below (Figure 2), as well as by gravimetric chemical analysis.

Description of the drawings

To complement the information and in order to help a better understanding, the following is accompanied as an integral part of the description:

Figure 1, a process diagram, shows the general scheme of the salt or brackish water treatment system object of this invention.

one-

Water to treat.

2-

Peroxide.

3-

Sulfuric acid.

4-

Catalyst.

5-

Secuestreno.

6-

Chlorine gas

7-

Liquefaction

8-

Water without chlorides, with soluble sulfates, magnesium and plaster.

9-

Synthetic plaster

10 -

Water without chlorides, with soluble sulfates and magnesium.

eleven -

Alkaline hydroxide

12 -

Magnesium hydroxide.

13 -

Water without chlorides, without magnesium and with soluble sulfates.

14 -

Chlorine-free calcium component.

fifteen -

Water with alkaline hydroxides and plaster.

16 -

Water with alkaline hydroxides.

17 -

Commercialization.

18 -

Pouring water.

19 -

Reuse in the phase as alkaline hydroxide.

Figure 2 shows the microphotographs carried out in approved laboratories of Higher Technical Schools and Colleges, in its Microscopy Center, which correspond to the sample of the precipitate obtained by treatment with sulfuric acid, of different concentrations, from the saline rejection of the treatment by Reverse osmosis of seawater, according to the procedure described in the first phase of this invention.

The obtained photomicrographs correspond to the solid precipitate treated, (conveniently prepared and dried with a laboratory oven, disintegrated and screened with Maya Light of 4 microns) subjected to transmission microscopy and X-ray diffraction thereof.

According to a report issued by the aforementioned centers, "it can be manifested in view of what has been obtained that is calcium sulfate dihydrate (synthetic gypsum)".

Description of a preferred embodiment

Within all types of salty or brackish waters where our invention can be applied, it will preferably have a direct application to treat seawater, and of course, the rejection water of desalination plants with very high salinity concentrations. Therefore, for the explanation of this process we have considered the type of rejection water treatment of desalination plants (1).

Starting from the physicochemical analyzes of the inlet water and the rejection water of a seawater desalination plant, we are going to describe the procedure to reduce the salinity of the rejection water to admissible limits and the parameters that affect the environment very negatively .

We start from the type of Mediterranean Sea Water, or other marine masses of similar characteristics. According to the chemical analyzes that we have carried out of the seawater obtained with the sampling “in situ”, 200 m from the shore of the Mediterranean Sea, at a depth of 1 m from the surface of the water, we obtain the results indicated Then we have contrasted with analyzes carried out by other approved laboratories, which have similar values.

We have also verified that these Results are obtained with the water captured in wells next to the beach (inland), 200 m deep, varying only some of the parameters, which do not substantially affect the treatment of salt water. They are the following:

From the contrast between the analysis the salt water taken directly from the sea, and those of the salt water taken from wells by the sea, we have found that there are small differences in the three parameters that we have considered more representative.

We verify that these differences are not substantial for the work we are developing, so it would not matter if it is sea water or a water that is in its vicinity.

On the other hand, the analyzes obtained from the rejection or brine water from a desalination station type are the following:

We only review, then, the parameters that we consider fundamental for the purpose of this invention, the rest of the parameters being inoperative, STD, sulfates, chlorides, calcium, magnesium and sodium.

Comparing these parameters in seawater or its proximity and rejection water, we can especially review:

•

The greater conductivity of the rejection water due to the existence of a greater amount of dissolved salts, going from 55,000 to 86,900 μS / cm.

•

Of the Total Dissolved Salts (STD), the amount existing in the rejection water is much greater, from 38,500 in the initial salt water to 72,055 mg / l in the rejection water.

•

Sulfate ions [SO4 ”] also suffer a large increase from 2,650 to 5,150 mg / l.

•

Chloride ions [Cl−] also represent a large increase from 19,200 to 37,440 mg / l.

•

Calcium cations [Ca ++] go from 481 to 950 mg / l.

•

Magnesium cations [Mg ++] go from 1,120 to 2,049 mg / l.

•

Sodium cations [Na +] go from 11,000 to 21,200 mg / l.

Once the differences between both inlet waters and the rejection of a desalination plant have been verified, the object of the invention is to treat the problem or rejection water (1) to obtain a water whose physicochemical characteristics are equal to or better than those of the inlet water (salt water of the Mediterranean Sea or similar), that is to say of equal or less salinity.

In the same way, if we can eliminate the salts in the rejection water, with a concentration much higher than the sea salt water, also with this process we can directly treat the salt or brackish water by decreasing the rejection water to limits compatible with its discharge to the natural environment without harmful effects to it.

The Modus operandi, according to the process diagram divided into several phases, is as follows:

1st Phase (initial water treatment with hydrogen peroxide and sulfuric acid in doses and concentrations suitable for obtaining water without chlorides with sulfates eliminating chloride ions).

The initial water (1) is treated with hydrogen peroxide (H2O2) (2) at the appropriate percentage by weight, sulfuric acid as an acidifying reagent and catalyst (3), together with a metal oxide catalyst (4), in order to eliminate quantitatively all the chlorides in the problem water transforming them into chlorine gas (6), which could industrially be used by subjecting it to high pressure and liquefying it (7).

As the problem water has a calcium ion presence, making the appropriate chemical reactions and the corresponding calculations, taking into account the concentration of the [Ca ++] ion in the mentioned 1,000 cc of water, a sufficient amount of sulfuric acid will be needed for the transformation of Chlorides [Cl−] and in the presence of a sequestrian type (titriplex) (5) that is capable of capturing calcium and magnesium ions, and at optimal precipitation we precipitate the synthetic plaster releasing the calcium ion and leaving the magnesium ion retained, we obtain chlorine gas (Cl2 ↑), and water without chlorides with soluble sulfates with the precipitate of synthetic gypsum (8), which is filtered by a physical process with a suitable mesh of light, thus obtaining a water without chlorides with soluble sulfates that would pass to the next phase (10). In this way we reduce salinity by removing the chloride and calcium ions from the initial water.

The amount of chlorine gas produced, starting from 37,440 mg of chlorides in 1,000 cc of the problem water, is between 25,000 and 40,000 mg.

The demonstration that we have completely oxidized the chloride ion [Cl−] to chlorine gas, Cl2 ↑, is done by checking in the water, after performing such transformation, the non-existence of the chloride ion by treating it with AgNO3N / 10 silver nitrate and as an indicator, potassium chromate K2CrO4 at 5 ‰, not even giving valuable clues.

2nd Phase (treatment of filtered water without chlorides with soluble sulfates and presence of magnesium ion, with alkaline hydroxide to obtain water with sulfates and reduce salinity by eliminating the magnesium ion).

The filtered water (10), from the previous phase, contains a concentration of magnesium ion [Mg ++] of

2,050 mg And it requires for its treatment an adequate amount of alkaline hydroxide (11), which is supplied achieving a precipitate between 4,000 and 6,000 mg of magnesium hydroxide (12), which by means of a physical procedure filtered through a light mesh suitable is separated, and obtaining water with soluble sulfates free of magnesium (13) that would pass to the next phase. Thus, we continue to reduce water salinity by eliminating magnesium ion in this process.

3rd Phase (water treatment with soluble magnesium-free sulfates with calcium components to eliminate sulfate ions).

Filtered water (13), from the previous phases, contains a concentration of sulfate ions [SO4 ”] between 50,000 and 60,000 mg. Which require an adequate amount of chlorine-free soluble calcium component (14), correcting the pH appropriately with sulfuric acid (3), we produce between 85,000 and 110,000 mg of synthetic gypsum (9), which precipitates and separates through a fi ltered as in the first phase, obtaining water with alkaline hydroxides (16) that can be reused in the second phase (19) or as commercial use (17) or poured into the receiving medium (18), due to the elimination of sulfate ions and the consequent reduction in initial salinity by an approximate percentage of 40-50%.

To demonstrate the total evidence that the precipitate obtained is, quantitatively, of the said synthetic plaster, we repeatedly wash the precipitated said with bidethylated water and verify with 25% BaCl2, BaCl2, the non-existence in said sulfate ion wash water . In addition, it has been proven that it is a synthetic plaster when performing through different microphotographs performed with a sample of dried solid disintegrated and sieved an X-ray diffraction analysis through an electron microscope in different standardized specialized laboratories.

The balance of dissolved salts before and after producing other salts and obtaining different chemicals is as follows. According to the rejection water analysis (1) we start from 72,055 mg / l of STD and at the end of the process that comprises the three phases described above is approximately 45,000 mg / l of STD, this water with alkaline hydroxides (16) it can be used in a percentage of 30% to introduce as part of the treatment in phase 2 (19), and the rest can be used for commercial use as water with an alkaline concentration at an approximate percentage of 40%, whereby no pouring water is obtained.

On the other hand, we establish a balance of the products obtained. If we start from 1000 cc of rejection water, in the whole process we obtain the following products:

one)

Between 25,000 and 40,000 mg of chlorine gas.

2)

Between 85,000 and 115,000 mg of synthetic plaster.

3)

Between 4,000 and 6,000 mg of magnesium hydroxide.

4)

Greater than 40,000 mg of alkaline salts.

In conclusion, we determine that the salinity of the starting water has been eliminated with an approximate yield of 100% in the case of zero discharge when the water with alkaline salts is used as a commercialized industrial product, with which the problem of rejection water that It is a threat to the natural environment is fully resolved and, on the other hand, we obtain proportions of useful products in the industry and in construction that can make the use of this process very profitable, on the other hand obtaining chlorine by a Non-aggressive system to the atmosphere can generate incalculable benefits for the protection of the environment.

Claims (11)

1. Chemical process of salt or brackish water treatment, mainly the rejection water of desalination plants (1), characterized in that it comprises the following phases: Phase 1.-The initial water (1) is treated with hydrogen peroxide (2), sulfuric acid (3) with a normal range between N / 10 and 5N, and a catalyst (4) at a pH between 5 and 7. Phase 2.- The filtered water of Phase 1 (13) is treated with chlorine-free calcium component (14) and sulfuric acid (3) with a normality in a range between N / 10 and 5N at a pH between 5 and 7 .

2.

Process according to claim 1 characterized in that the initial water (1) does not have calcium or magnesium ions.

3.

Process according to claim 1 wherein the initial water (1) has calcium but not magnesium ions.

Four.

Chemical process for the treatment of salt or brackish water according to claim 3, characterized in that in phase 1 a sequestrene of the titriplex type (5) is used.

5. Process according to claim 1 wherein the initial water (1) has calcium and magnesium ions.

6.

Chemical process of salt water treatment according to claim 5, characterized in that in phase 1 a sequestrene of the titriplex type (5) capable of retaining calcium and magnesium ions is used, and where additionally, in phase 1a, the water is treated fi ltration of phase 1 (10) with alkali hydroxides (11).

7.

Chemical process according to claim 1 characterized in that the treated water (1) comes from the rejection of a desalination plant, the sea, a natural brackish water well, a lake or a brackish water river.

8.

Chemical process according to claim 1 characterized in that the chlorine-free calcium component (14) is selectable from a group consisting of calcium carbonate, quicklime, calcium bromide, calcium iodide or calcium hydroxide.

9.

Chemical process according to claim 1 characterized in that hydrogen peroxide (2) with a weight percentage between 20 and 50% is used in the first phase.

10. Chemical process according to claim 1 characterized in that the catalyst (4) is of the metal oxide type. SPANISH OFFICE OF THE PATENTS AND BRAND Application no .: 201001317 SPAIN Date of submission of the application: 14.10.2010 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: C02F1 / 52 (2006.01) C02F103 / 08 (2006.01) RELEVANT DOCUMENTS

Category

56 Documents cited Claims Affected

TO

US 4180547 A (ECODYNE CORP) 25.12.1979, 1-10

column 1, line 42 - column 3, line 40.

TO

US 3925028 A (FERNANDEZ LOZANO JOSE ANTONIO) 09.12.1975, 1-10

column 1, line 6 - column 3, line 14.

TO

EP 0382876 A1 (NASU ATSUSHI) 22.08.1990, 1-10

page 2, line 45 - page 3, line 26.

TO

ES 2340452 A1 (SADYT) 02.06.2010, 1-10

page 2, line 64 - page 3, line 31.

TO

EN 2332856 A1 (PORCAR ORTI JAVIER) 12.02.2010, 1-10

page 2, line 52 - page 3, line 5.

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims • for claims no:

Date of realization of the report 21.02.2012

Examiner M. García González Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 201001317 Minimum documentation sought (classification system followed by classification symbols) C02F Electronic databases consulted during the search (name of the database and, if possible, terms of search used) INVENES, EPODOC, WPI, TXT, XPESP, NPL State of the Art Report Page 2/4  WRITTEN OPINION Application number: 201001317 Date of Written Opinion: 21.02.2012 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims 1-10 Claims IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims 1-10 Claims IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 201001317 1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

US 4180547 A (ECODYNE CORP) 25.12.1979

D02

US 3925028 A (FERNANDEZ LOZANO JOSE ANTONIO) 09.12.1975

D03

EP 0382876 A1 (NASU ATSUSHI) 08/22/1990

2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The object of the invention is a process for the treatment of salt water by means of which various commercial chemicals are obtained. Document D01 discloses a procedure for the recovery of chemical products from saline water in several stages, finally obtaining potable water and several commercial chemicals: NaCl, KCl, Na2SO4 and calcium and magnesium compounds. (see column 1, line 42 - column 3, line 40) Document D02 discloses a process for the recovery of potassium and magnesium salts from brines by the addition of methanol, forming an insoluble precipitate that can be used as fertilizer. (see column 1, line 6 - column 3, line 14) Document D03 refers to a method for recovering salts contained in seawater in which the water is brought to an acidic pH by the addition of sulfuric acid, then a strong alkaline agent is added to bring the pH to a value. raised and the precipitate formed is removed. (see page 2, line 45 - page 3, line 26) None of the aforementioned documents or any relevant combination thereof discloses a procedure for the treatment of salt water in which said water is treated in a first stage with hydrogen peroxide, sulfuric acid and a catalyst, and in a second stage the filtering the above with a calcium component free of chlorine and sulfuric acid, as set out in claim 1 of the application, so that a water with low salt content and various chemical products of commercial interest is obtained: synthetic plaster, magnesium hydroxide and chlorine gas. Consequently, the invention as set forth in claims 1-10 of the application is new and is considered to imply inventive activity (Art. 6 and 8 LP). State of the Art Report Page 4/4