ES2423255A1 - Process for the elimination of the haloanisoles and halophenols present in cork and installation to carry out said elimination - Google Patents

Abstract

The present invention belongs to the field of processes for the elimination of the haloanisoles and halophenols present in cork as well as of the installations used to carry out said elimination, where the process for the elimination of halogenated compounds derived from anisole and phenol present in cork is based on the thermal desorption in gaseous state of said compounds of the cork by the application of vacuum as well as the installation where said process is performed.

Description

Procedure for the elimination of haloanisols and halophenols present in the cork and installation to carry out said elimination

OBJECT OF THE INVENTION

The present invention belongs to the field of procedures for the elimination of haloanisols and halophenols present in the cork as well as the facilities used to carry out said elimination.

The main object of the present invention is a process for the elimination of halogenated compounds derived from anisole and phenol present in the cork based on the thermal desorption in the gaseous state of said cork compounds by means of the application of vacuum, as well as the installation where The above procedure is carried out.

BACKGROUND OF THE INVENTION

Cork is a natural material, coming from the bark of a tree called "Quercus Suber". Its cellular structure is formed by dead units filled with air, arranged very regularly.

Normally its chemical composition varies depending on the type of cork, its origin and the age of the tree. The most common components of cork are: the suberine (of the order of 46%), which is responsible for the high compressibility and elasticity of the cork; lignin (25%), cellulose and other polysaccharides (12%), zeroide substances (6%), which are primarily responsible for the impermeability of cork, tannins (6%), and other compounds (5%).

Its chemical composition, together with its characteristic structure provide the cork with physical properties that make it a material with multiple applications, among which the manufacture of stoppers for the closure of containers, for example bottles of wine, brandy, champagne, champagne, stands out. whiskey, etc. In this application, it is essential that the cap respects the organoleptic characteristics of the contents of the package.

In this sense, the cork industry has suffered what is called "cork flavor", that is, the appearance of an unpleasant taste and / or aroma in drinks whose bottles have been sealed with cork stopper. This smell

or taste, when present, deteriorates the quality of the contents of the bottles, which implies significant economic losses for the industries.

Nowadays, it is well known that the substances responsible for this effect are halogenated compounds derived from anisole. These include 2,3,4,6-tetrachloroanisole (TeCA), pentachloroanisole (PCA), 2,4,6-tribromoanisole (TBA), but especially 2,4,6-trichloroanisole (TCA).

All these haloanisols are very polluting, capable of ruining the organoleptic properties of any liquid, producing unpleasant odors and flavors, which we could call fungal or moldy. This is very possibly due to its high volatility. Its threshold of olfactory and gustatory perception is very low, so that a very small amount is already perceived through taste or smell. In the case of TCA, 1.5-3 ng / l of said compound in an alcoholic solution such as wine, is sufficient to be detected.

Contamination by haloanisols has its origin in other compounds, halophenols. These substances have been widely used as pesticides, despite being very polluting and lasting in the atmosphere for long periods of time. Therefore, halophenols can be found as contaminants in both water and soil and in the atmosphere. Given the high toxicity of these compounds, some microorganisms present in the cork cannot degrade them when they come into contact with these compounds, so they transform them into haloanisols, through a biomethylation reaction. For all this, it can be said that the true origin of cork contamination by haloanisols is a problem of environmental pollution.

The economic losses suffered by industries around the world from pollution with haloanisols are enormous and difficult to calculate. Therefore, there is a growing interest in removing these pollutants from cork. Despite the enormous effort being made to solve this problem, there is currently no treatment that is totally effective, having developed different strategies, such as avoiding the formation of haloanisols, preventing the migration of the haloanisols to the liquid or eliminating the haloanisols. existing in the cork.

A process based on washing the plug with an aqueous solution of alkaline nature is detailed in document ES2076185, in order to avoid the formation of haloanisols by eliminating the microorganisms that produce them.

A similar procedure is described in the patent ES2255458, which raises the inhibition of the substances causing the bad smell, by adding and enriching the cork with carbonate and bicarbonate salts of alkali and alkaline earth metals. In this case, the invention is based on causing a chemical change that causes the microorganisms to change, with the consequent inhibition of the formation of haloanisols.

Microwave radiation has been proposed in order to remove the haloanisols from the cap in the ES2310030 patent where it is said that the action of this radiation manages to sterilize the cork and consequently reduce its contamination. The process tries to go beyond, treating not only the surface, but applying a variable power tries to reach inside the cork.

There are other techniques through electron accelerators that carry out, through emissions �, the elimination of microorganisms with the consequent total sterilization of the cork stopper.

The use of physical barriers to prevent haloanisols from coming into contact with the liquid is another of the strategies used. Within this field, is the document ES2148796 whose procedure is based on coating the cork stopper, or derivative of the cork, with a substance, generally silicone, that prevents the contaminating substances from the plug from coming into contact with the packed liquid.

All these procedures are aimed at preventing the formation of the contaminant or that it comes into contact with the packed liquid, but none of them is capable of eliminating haloanisols and other existing contaminants. To solve this problem, different alternatives based on different physical chemical principles have been proposed.

A removal procedure based on an adsorption process has been proposed in WO01 / 41989. This consists of eliminating the contaminant present in the cork, by contact with an aqueous suspension of activated carbon, from coconut shell. Adequate conditions will favor the migration of the contaminant towards activated carbon, being adsorbed on it.

Another seemingly effective physical chemical principle for the removal of contaminants is extraction. In this context, the procedures that have been proposed are numerous.

In ES2216965, the extraction is carried out with a dense fluid, proposing CO2 as more appropriate. In accordance with this invention, the CO2 under pressure (100-300 bar), is brought into contact with the cork at a certain temperature (40-80 ° C), thus eliminating unwanted substances. This procedure also extracts numerous compounds existing in the cork, so it is advisable to add a cosolvent to improve the selectivity of the extraction. The main drawback of this procedure is its high cost.

A variant of this method can be considered in EP2033751, in which an inert gas (carbon dioxide, nitrogen or noble gases such as argon or mixtures) is used to treat cork for the same purpose. In this case, the pressure conditions at which the process is carried out are moderate, making the procedure significantly cheaper.

On the other hand, the extraction of haloanisols with water vapor has become one of the most common procedures, with numerous variants being proposed.

A widely known procedure is that set out in document ES2268459, where significant extraction of compounds present in the cork, in particular TCA, is carried out by steam distillation. Vapor and water at a certain pressure (below 0.8 bar) allow to expel the contaminants present inside the cork cells. This procedure is similar to that set out in the ES2019562 patent, with the proviso that the former allows cork to be treated in all its varieties, both granulated cork and discs and caps, while the latter is only considered valid for small cork. In addition, the latter includes some additional stages, such as crushing, preheating and cooling of the cork.

Another process that uses water vapor for the extraction of the contaminant is described in the patent ES2237133. In this case, the process is favored by the use of pressurized steam (2-30 bar). The duration of the treatment is short, less than 1 minute and is followed by a rapid and brutal expansion, until the vessel reaches atmospheric pressure.

Another way to favor steam extraction is by including other components in the stream. Thus, the ES2247180 patent contemplates the use of gaseous mixtures consisting of water vapor and an organic solvent, specifically ethanol, in the presence of air and semi-continuously.

Patent ES2259547 proposes the removal of contaminants by a process based on the extraction with a liquid, generally water or water with surfactants, which is developed in three stages. In the first, the cork comes into contact with the liquid, providing heat energy and creating a vacuum environment (low pressure). This depression causes air bubbles trapped in the pores of the cork to escape outward, thereby facilitating the entry of the liquid destined for decontamination. In the second stage the cork is left at rest and in the third stage it is dried using different methodologies known in the sector.

In addition, the threshold of olfactory and gustatory perception of haloanisols is so low (for example in the case of TCA 1.5-3.5 ng / l in a hydroalcoholic solution (wine) is sufficient to be detected) that elimination levels of Cork haloanisols so high that most of the previously proposed methods fail to achieve.

On other occasions, the cost of the facilities, the processing and the energy used are so high that they make many of the proposed procedures unfeasible.

On the other hand, cork is a delicate material, with a structure, chemical composition and very defined properties. Energetic treatments, in which high temperatures and / or pressures are used, end up producing important alterations and degradations in their structure and composition. Others, methods based on the extraction of pollutants with liquid solvents (water, ethanol, etc.) or gaseous solvents (water vapor, CO2, etc.) eliminate, together with pollutants, other valuable components of cork, such as waxes, suberine , tannins, etc., thus altering its properties.

On other occasions, in which substances are used for the elimination of pollutants, they end up contaminating the cork.

The applicant is unaware of the existence of treatments that meet the necessary conditions for the elimination of the haloanisols present in the cork effectively, for all forms of cork, both in large pieces and granular, without having to carry out a previous dissolution in a liquid or a supercritical fluid for the subsequent extraction of the contaminants, and where said procedures do not produce alterations in the structure and chemical composition of the cork.

DESCRIPTION OF THE INVENTION

The present invention relates to a process for the elimination of haloanisols and halophenols present in the cork comprising a step of thermal desorption in the gaseous state of the haloanisols and halophenols present in the cork by applying a vacuum pressure.

In order to ensure and ensure that the haloanisols and halophenols are in a gaseous state, the desorption stage must occur at a temperature higher than the boiling temperature of said contaminating compounds, that is, of the haloanisols and halophenols, temperatures that vary depending on the vacuum pressure applied to the cork.

The melting and boiling points of said contaminating compounds decrease rapidly when the pressure is reduced, so that if it is very low, the compounds will be in a gaseous state at relatively low temperatures. Table 2 shows how the boiling point of 2,4,6-trichloroanisole (TCA) changes with pressure. According to these data, the TCA at a pressure of 0.1 mbar would be in a gaseous state at 19.5 ° C; at 1 mbar it would require 56 ° C; at 10 mbar 98 ° C and at 1000 mbar 239 ° C. So, the

The thermal desorption of these pollutants is possible at moderate temperatures, if very low pressures are used.

Table 1 shows these points for the most frequent haloanisols and halophenols in cork. In general they are compounds with high boiling points that increase as the number of substituted chlorines in the molecule increases. Haloanisols have slightly lower melting and boiling points than halophenols, so they are somewhat more volatile.

Table 1. Melting and boiling points of halophenols and haloanisols at atmospheric pressure. fifteen

Compound

Tª fusion (ºC) Boiling temperature (ºC)

2,4,6-trichlorophenol (TCF)

69.5 246

2,3,4,6-tetrachlorophenol (TeCF)

115 288

pentachlorophenol (PCF)

190 310

Tribromophenol (TBF)

95 286

2,4,6-trichloroanisole (TCA)

60-62 240

1,2,3,5-tetrachloroanisole (TeCA)

280

pentachloroanisole (PCA)

305

Tribromoanisole (TBA)

88 298

These melting and boiling points decrease rapidly when the pressure is reduced below atmospheric pressure, that is, under vacuum conditions, so that if it is very low, the compounds will be in

20 gaseous state at relatively low temperatures. Table 2 shows how the boiling point of the TCA changes with the pressure. According to these data, the TCA at a pressure of 0.1 mbar would be in a gaseous state at 19.5 ° C; at 1 mbar it would require 56 ° C; at 10 mbar 98 ° C and at 1000 mbar 239 ° C. Thus, the thermal desorption of these contaminants is possible at room temperature, if vacuum pressures of the order of 0.01 mbar are used.

Table 2. Evolution of the boiling temperature of 2,4,6-trichloroanisole (TCA) with pressure.

Pressure (mbar)

Boiling temperature (ºC)

0.05

10

0.10

19.5

0.50

44.5

one

56

10

98

100

157

500

215

1000

239

These vacuum conditions in the desorption process are not only aimed at lowering the boiling point of the haloanisols and halophenols present in the cork, but also displacing the adsorption-desorption equilibrium established in favor of desorption.

The contaminants remain in the cork structure adsorbed on their surface in accordance with the

5 following dynamic equilibrium: desorption

CORK WITH CONTAMINANT CORK + CONTAMINANT (GAS)

adsorption

This balance is shifted in favor of desorption as the vacuum conditions remove the molecules of the haloanisols and halophenol contaminants that are desorbed from the cork structure. This shift in equilibrium in favor of desorption is also favored by an increase in temperature, since with heat the bonds that hold the pollutants together to the surface of the cork are broken. These bonds can be strong, so not only do you need to reach a certain temperature so that the contaminant is in a gaseous state, but a somewhat higher temperature is needed to break those bonds.

The invention also relates to the installation for carrying out the process for removing haloanisols and halophenols present in the cork described above.

The installation comprises a tank where the cork to be treated is placed, a tank that is capable of withstanding vacuum pressure conditions of up to at least 0.01 mbar. The tank in turn comprises a cork heating device.

The installation further comprises a vacuum application device that is connected to the reservoir for the application of vacuum pressure.

The cork on which the procedure for the elimination of haloanisols and halophenols described above is applied and which is contained in the tank of the installation described above can also be presented in any shape and size: pieces of bark, plates, discs, plugs, granules, etc.

The main advantages of the process and the installation of the present invention with respect to the known procedures and installations are:

•

It is a simple and easy procedure to carry out since it is done in a single stage.

•

No additional substance is used during the process, so there is no possibility of cork contamination.

•

The installation costs are very low compared to those of other procedures, such as extraction with supercritical CO2, water vapor, etc.

•

The handling and energy costs are very small, since the temperatures at which the cork is heated are low and in some cases they may not exist. On the other hand, the energy costs to make the corresponding vacuum are always very low.

•

It allows to treat large volumes of cork in a single treatment without overheating the installation, making the process very economical. Deposits of 10, 20 m3 and larger can be easily used.

•

The control over the temperature and the vacuum allow in turn to easily control the cleaning process of the cork, avoiding its degradation and the elimination of valuable substances such as waxes, tannins, etc.

•

It can be applied to any format and size of the cork such as: bark pieces, large plates, discs, plugs, granular cork, etc.

•

It can be used with cork fresh from the tree and before or after mechanical and / or chemical treatments generally known and common in cork processing, such as boiling

or hot water treatment.

•

It can be used after other cork purification treatments that due to their limitations cannot reach the desired degree of cleanliness.

DESCRIPTION OF THE DRAWINGS

To complement the description that is being made and in order to help a better understanding of the characteristics of the invention, according to a preferred example of practical implementation thereof, a set of drawings is attached as an integral part of said description. where, for illustrative and non-limiting purposes, the following has been represented:

Figure 1.- Shows a schematic view of the installation for the elimination of haloanisols and halophenols present in the cork of the present invention.

5 PREFERRED EMBODIMENT OF THE INVENTION

A preferred and never limiting embodiment of the process for the elimination of haloanisols and halophenols present in the cork of the present invention, as well as the installation for carrying out said elimination process, is described below.

The elimination process comprises a stage of thermal desorption in the gaseous state of the haloanisols and halophenols of the cork by applying a vacuum pressure. Preferably, the vacuum pressure is in the range between 1000 mbar and 0.01 mbar, and the temperature between 310 ° C and 0 ° C, whereby the procedure would eliminate the following compounds at a level by

15 below the threshold of olfactory and gustatory perception in case the cork is used as a stopper for a bottle of an alcoholic solution such as wine:

2,4,6-trichlorophenol (TCF)

2,3,4,6-tetrachlorophenol (TeCF)

pentachlorophenol (PCF)

Tribromophenol (TBF)

2,4,6-trichloroanisole (TCA)

1,2,3,5-tetrachloroanisole (TeCA)

pentachloroanisole (PCA)

Tribromoanisole (TBA)

where the threshold of perception for the above compounds is located at 1.5-3 ng / l of compound in an alcoholic solution such as wine.

More preferably, the vacuum pressure is in the range between 1000 mbar and 0.01 mbar, and the temperature for thermal desorption in the cork between 246 ° C and 0 ° C, thereby eliminating the following compounds at a level below the threshold of olfactory and gustatory perception in case of

25 that the cork be used as a stopper for a bottle of an alcoholic solution such as wine:

2,4,6-trichlorophenol (TCF)

2,4,6-trichloroanisole (TCA)

where the threshold of perception for the above compounds is located at 2.5 ng / l of compound in an alcoholic solution such as wine.

More preferably, the selective removal of 2,4,6-trichloroanisole (TCA) is carried out by applying a vacuum pressure of 0.1 mbar with thermal desorption temperature conditions of at least 19.5 ° C; or by applying a vacuum pressure of 1 mbar with thermal desorption temperature conditions of at least 56 ° C; or by applying a vacuum pressure of 10 mbar with temperature conditions of at

35 minus 98 ° C or by applying a vacuum pressure of 1000 mbar with thermal desorption temperature conditions of at least 239 ° C, in addition to any pressure-temperature pair included in the previous extreme values and proportional to them and that An expert in the field would be able to formulate in view of the above values.

40 Temperatures and voids in which the haloanisols did not reach the boiling point, but the melting point could also be used. In this case, the haloanisole would be in a liquid state, although there would always be a liquid-gas balance.

desorption

CORK WITH CONTAMINANT (Liquid)

CORK + CONTAMINANT (Gas)

adsorption

In this way, since there is a continuous vacuum that removes the contaminant (gas), the cork would end up free of contaminant.

Under these conditions of vacuum and temperature, in which the contaminant contained in the cork would be in a liquid state, the desorption process is much slower and less effective than when vacuum and temperature are used to ensure that the contaminant is in the gas state; So the use of these voids and temperatures are less recommended.

The time of the desorption stage is another variable that can be controlled in said procedure. The longer the cork is subjected to the thermal desorption stage, the greater the degree of elimination of the haloanisols and halophenols.

In summary, it can be said that the thermal desorption process can be controlled based on temperature, pressure and treatment time.

These three variables allow operating in very different conditions:

•

With high temperatures and large voids, the treatment time is shortened since the process is fast. However, under these conditions you can also desorb other less volatile substances that are present in the cork, such as waxes, tannins, etc., and if the temperature is very high the cork can suffer degradation.

•

With low temperatures and small voids the time is extended and the less volatile contaminants may not be completely eliminated, however the structure and chemical composition of the cork will remain very stable.

•

Intermediate temperatures and large voids may be the most recommended conditions.

Pressures below atmospheric, up to 0.05 mbar and even lower, can be used. However, very large voids are hard to come by and require more expensive equipment.

On the other hand, the cork is quite stable up to temperatures of 135 ° C, so higher temperatures can only be used for short periods of time. Temperatures between 100 and 135 ° C are the most recommended. Lower temperatures, even up to 0 ° C, can be used, although the treatment time is extended, but they have the advantage that the energy cost of heating the cork is reduced or disappears. In this way the range of usable temperatures preferably ranges from 0 ° C to about 240 ° C.

Another important aspect to consider is the amount of water retained by the cork. The cork in a natural way, can retain water from environmental humidity, or from previous treatments to which it has been subjected, such as boiling, steam extraction, etc., reaching values of 3-15%.

Since the water is a compound with a boiling point well below that of the haloanisols and being in major quantities against these, during the process of thermal desorption under vacuum, it is preferably desorbed, consuming a large amount of energy during the process. Therefore, it is advisable to apply the vacuum thermal desorption treatment with a cork that does not exceed a moisture content of 20%.

Previous studies carried out in the laboratory have shown that the efficiency and speed of thermal vacuum desorption is greater if the pollutants present in the cork (haloanisoles and halophenols) have undergone a recrystallization process, by means of a boiled of the cork in water and later dried, immediately before the thermal desorption, whereby the haloanisols and halophenols are in a recrystallized state.

EXAMPLE 1.

The following results were obtained in several laboratory tests:

Granular cork with a TCA contamination of 10.43 ng / l was used.

Applying the process of the invention for 10 hours at 100 ° C and at a pressure of 0.1 amber, its TCA level was reduced to 2.5 ng / l.

Applying the process of the invention for 10 hours at 115 ° C and at a pressure of 0.1 amber, its TCA level was reduced to 2.3 ng / l.

Applying the process of the invention for 15 hours at 100 ° C and at a pressure of 0.1 amber, its TCA level was reduced to 0.3 ng / l,

all of them below the threshold of perception of the TCA in an alcoholic solution such as wine.

Figure 1 shows the scheme of an installation to carry out thermal desorption under vacuum conditions of the haloanisols and halophenols present in the cork of the removal procedure described above.

The installation comprises a tank (1) where the cork (3) to be treated is placed, tank (1) that is capable of withstanding vacuum pressure conditions of up to at least 0.01 mbar. The tank (1) in turn comprises a heating device (2) for the cork (2), which is preferably a heat exchanger. The deposit

(1) It is thermally insulated to minimize heat losses and thus reduce heating costs.

The installation further comprises a vacuum application device (5), which is preferably a vacuum pump, which is connected to the tank (1).

The installation further comprises a device for collecting (4) the desorbed contaminants, that is, for the haloanisols and halophenols, which is arranged between the tank (1) and the vacuum application device (5) whose mission is to collect the contaminants and any other exorbitant substance. This prevents contaminants from being emitted abroad and becoming a new source of cork contamination. It also serves as a protection filter for the vacuum application device (5) that could be damaged by desorbed substances. This collection device (4) for the desorbed contaminants can be a condenser, a cold trap, an adsorbent bed, or the like.

Claims (21)

1.- Procedure for the elimination of haloanisols and halophenols present in the cork characterized in that it comprises a stage of thermal desorption in the gaseous state of the haloanisols and halophenols present in the cork by applying a vacuum pressure. 2. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 1 characterized in that the vacuum pressure is in the range between 1000 mbar and 0.01 mbar with a temperature of thermal desorption in the cork between 310 ° C and 0 ºC. 3. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 2 characterized in that the vacuum pressure is in the range between 1000 mbar and 0.01 mbar with a thermal desorption temperature in the cork between 246 ° C and 0 ºC. 4. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 3 characterized in that the vacuum pressure is 0.1 mbar with a thermal desorption temperature of at least 19.5 ° C. 5. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 3 characterized in that the vacuum pressure is 1 mbar with a thermal desorption temperature of at least 56 ° C. 6. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 3 characterized in that the vacuum pressure is 10 mbar with a temperature of at least 98 ° C. 7. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 3 characterized in that the vacuum pressure is 1000 mbar with a thermal desorption temperature of at least 239 ° C. 8. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 4 characterized in that the thermal desorption step is applied for 10 hours at 100 ° C and at a pressure of 0.1mbar to reduce the content of 2,4,6 -trichloroanisole (TCA) of 10.43 ng / 2.5 ng / l. 9. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 4 characterized in that the thermal desorption step is applied for 10 hours at 115 ° C and at a pressure of 0.1mbar to reduce the content of 2,4,6 -trichloroanisole (TCA) of 10.43 ng / 2.3 ng / l. 10. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 4 characterized in that the thermal desorption step is applied for 15 hours at 100 ° C and at a pressure of 0.1mbar to reduce the content of 2,4,6 -trichloroanisole (TCA) of 10.43 ng / 0.3 ng / l. 11. Procedure for the elimination of haloanisols and halophenols present in the cork according to any of the preceding claims characterized in that the cork is presented in the form of a piece of bark, plate, disc, plug or granules. 12.-Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 11 characterized in that the cork has a moisture content of up to 20%. 13. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 1, characterized in that it comprises an additional step of recrystallization of the haloanisols and halophenols, prior to thermal desorption. 14. Procedure for the elimination of haloanisols and halophenols present in the cork according to claim 13, characterized in that the recrystallization comprises boiling in water and subsequent drying of the cork. 15.- Installation for carrying out the method of eliminating haloanisols and halophenols present in the cork of any of the preceding claims characterized in that it comprises a tank (1) where the cork (3) to be treated and a device for applying empty (5) that is connected to the tank (1) for the application of vacuum pressure. 16.- Installation for carrying out the process of elimination of haloanisols and halophenols present in the cork according to claim 15 characterized in that the tank (1) in turn comprises a heating device (2) of the cork. 17. Installation for carrying out the process of elimination of haloanisols and halophenols present in the cork according to claim 16 characterized in that the cork heating device (2) (2) is a heat exchanger. 18. 18. Installation for carrying out the process of elimination of haloanisols and halophenols present in the cork according to claim 17 characterized in that the tank (1) is thermally insulated. 19. Installation for carrying out the process of elimination of haloanisols and halophenols present in the cork according to claim 15 characterized in that the vacuum application device (5) is a vacuum pump or an ejector. 20. Installation for carrying out the process of elimination of haloanisols and halophenols present in the cork according to any of claims 15 to 19 characterized in that it further comprises a device 20 for collecting (4) the desorbed contaminants disposed between the tank (1 ) and the vacuum application device (5). SPANISH OFFICE OF THE PATENTS AND BRAND Application no .: 201230373 SPAIN Date of submission of the application: 13.03.2012 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: B27K7 / 00 (2006.01) B67B1 / 03 (2006.01) RELEVANT DOCUMENTS

Category

56 Documents cited Claims Affected

TO

WO 2005025825 A1 (DEGUSSA et al.) 03/24/2005, claims. 1-20

TO

WO 2010040949 A1 (UNIV LA ROCHELLE et al.) 04.04.2010, claims. 1-20

TO

WO 2004004995 A1 (GODOY VARO JOSE LUIS) 15.01.2004, claims. 1-20

TO

ES 2247180 T3 (INST SUPERIOR TECNICO et al.) 01.03.2006, claims. 1-20

TO

EP 1216123 A1 (COMMISSARIAT ENERGIE ATOMIQUE et al.) 06.26.2002, claims. 1-20

TO

ES 2268459 T3 (AMORIM & IRMAOS S A) 16.03.2007, claims. 1-20

TO

ES 2216965 T3 (COMMISSARIAT ENERGIE ATOMIQUE et al.) 01.11.2004, claims. 1-20

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 04.03.2013

Examiner I. Abad Gurumeta Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 201230373 Minimum documentation sought (classification system followed by classification symbols) B27K, B67B Electronic databases consulted during the search (name of the database and, if possible, terms of search used) INVENES, EPODOC State of the Art Report Page 2/4  WRITTEN OPINION Application number: 201230373 Date of Written Opinion: 04.03.2013 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims Claims 1-20 IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims Claims 1-20 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: 201230373  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

WO 2005025825 A1 (DEGUSSA et al.) 03/24/2005

D02

WO 2010040949 A1 (UNIV LA ROCHELLE et al.) 04.15.2010

D03

WO 2004004995 A1 (GODOY VARO JOSE LUIS) 01.01.2004

D04

ES 2247180 T3 (INST SUPERIOR TECNICO et al.) 01.03.2006

D05

EP 1216123 A1 (COMMISSARIAT ENERGIE ATOMIQUE et al.) 06.26.2002

D06

ES 2268459 T3 (AMORIM & IRMAOS S A) 03/16/2007

D07

ES 2216965 T3 (COMMISSARIAT ENERGIE ATOMIQUE et al.) 01.11.2004

 2. Statement motivated according to articles 29.6 and 29.7 of the Regulation of execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The invention relates to a process and its installation for the elimination of haloanisols and halophenols present in the cork by thermal desorption in a gaseous state by applying a vacuum pressure (claims 1 and 15), for a pressure between 1000mbar and 0, 01 mbar and temperature between 310 ° C and 0 ° C, indicating preferences of operating conditions in these ranges (claims 2-7), as well as operating times to decrease the concentrations of 2, 4, 6, -trichloroanisole (claims 8-10). In addition, an additional step of recrystallization of haloanisols and halophenols prior to thermal desorption for a specific raw material is described (claims 11-14). The installation for carrying out said procedure is also described (claim 15-20) D01 refers to the purification of cork material to remove organic compounds, waxes and fats, by isobaric extraction with compressed gas with combined charge with adsorbent, at 10-120ºC and between 10 and 600 bar. (See claims) D02 refers to the extraction of aromatic molecules from the cork to obtain a cork flavor, by means of a thermo-hydro-mechanical treatment, which comprises subjecting the cork to at least a heating and pressurization of fluid for a reduced time and then subjecting it to a reduced pressure drop. (See claims) D03 refers to a cork decontamination and relaxation procedure for the elimination of microorganisms, spores, moldy parts and compounds of the organochlorine family, in particular 2,4,6-trichloroanisole (TCA), TCP, PCP and other chlorinated derivatives including one or more cycles each of which comprises: a) contacting cork to be decontaminated for a predetermined time with a fluid with or without additives; and b) drying said cork, said step a) being carried out inside a sealed tank, where the cork is immersed in said fluid and under conditions of higher than atmospheric pressure and preferably providing heat energy to said sealed tank. (See claims) D04 refers to a procedure for the extraction of foreign odors in cork stoppers or plates, characterized in that a gas mixture is used that is basically water vapor and steam of an organic solvent, in the presence of air, semi-continuously . (See claims) D05 refers to a cork decontamination procedure, for the elimination of components (halophenols and haloanisols) that affect the taste, such as those of wine bottle stoppers, by contacting a dense fluid under pressure, such as dioxide of carbon, operating at 10-120º © and 10-600 bars. (See claims). D06 refers to a process of treatment of cork products by extraction of compounds entrained in water vapor, for deodorization and elimination of haloanisols. (See claims). D07 refers to a process of removing unwanted substances from cork by extraction with dense fluid. (See claims) 1. NEW (ART. 6.1 Law 11/1986) AND INVENTIVE ACTIVITY (ART. 8.1 Law 11/1986) Documents D01-D07 reflect the closest state of the art. All these documents, although they show procedures for the elimination of unwanted compounds in the cork, in none of them does it refer to a process of elimination of halofenoles and haloanisoles of the cork by thermal desorption in a gaseous state by means of the application of vacuum claimed in invention. Therefore, the object of claims 1-20 meets the requirements of novelty and inventive activity in accordance with Article 6.1 and 8.1 of Law 11/1986. State of the Art Report Page 4/4