JP4370368B2 - Method for regenerating inorganic porous particles, water purification method, and continuous water purification device - Google Patents

Description

  The present invention relates to a method for regenerating inorganic porous particles, a method for purifying water, and a continuous water purifier, and the purpose thereof is to use ammonia and amine components contained in water and water vapor in a compact facility. A method for regenerating inorganic porous particles and a method for purifying water, which can be easily applied as a water recycling system even in special environments such as space environments, by safely removing chemicals without using any chemicals. Another object is to provide a continuous water purifier. In this specification, a smaller pressure value means a higher vacuum pressure, and a larger pressure value means a lower vacuum pressure.

  In recent years, manned space flight by space ships such as space shuttles has been frequently performed, and the construction of an international space station is also planned. When an astronaut stays in space for a long period of time, the biggest problem is securing water. At present, the water necessary for the astronaut's life is covered by water produced by fuel cells and water replenished by launching from the ground. However, the amount of water supplied by the fuel cell is limited, and launching water from the ground costs about 2.5 million yen per kg of water, and it is difficult to supply a large amount from the ground. For this reason, securing water in the space environment has become a major issue due to the prolonged stay in space and the increase in crew.

Therefore, research is currently being carried out to purify and reuse wastewater and urine dumped in space from space facilities. Currently, as this recycling apparatus, apparatuses using a reverse osmosis membrane method and a membrane distillation method are being studied. However, since the reverse osmosis membrane method has a low impurity removal efficiency, it requires a multi-stage process, which has the disadvantage of increasing the size of the apparatus. In addition, since high pressure is required, there is a risk of explosion, and it cannot be easily applied under special conditions such as a limited space facility and space environment. The membrane distillation method using a porous hydrophobic membrane is a method similar to the pervaporation membrane method. The membrane distillation method is a method of separating by a vapor pressure difference that becomes a driving force of permeation of each component, and the vapor pressure difference that becomes the driving force is given by a temperature difference between the membranes. Since the membrane used in the membrane distillation method has pores, if the permeation side is reduced in pressure as in the pervaporation membrane method, the membrane permeates without being separated. The weak point of the membrane distillation method is that the surface of the porous hydrophobic membrane becomes hydrophilic due to long-term operation, and the liquid can permeate the membrane as it is. The proximity of the module complicates the structure of the module and makes it difficult to reduce the weight, and the permeation flow rate is small.
This method could not be easily applied to space facilities and space environments of limited size.

  The present inventors have studied a method of reusing wastewater, urine, etc. that can be used in a limited space of a space facility, which does not use any chemicals and is simple and sufficient. First, a method using inorganic porous particles such as silica gel was examined as a method for separating impurities conventionally used. This method has a high resolution. However, this method has a problem that the regeneration performance is necessarily required for long-time use because the adsorption performance is lowered by using for a long time. It is common to use a solvent for the regeneration of inorganic porous particles, but the use of chemicals (solvents) in the space environment will generate new waste. I couldn't. Therefore, as a result of intensive studies, the present inventors studied the problem of regenerating inorganic porous particles without using any chemicals. Along with this problem, unlike the reverse osmosis membrane method, there is a pervaporation method as a membrane separation method that does not require conditions involving danger such as pressurization and can downsize the apparatus. It was a research subject. This pervaporation method is a separation method involving a phase change in which the supply side (primary side) is liquid and the permeation side (secondary side) is gas via a permeable membrane. The conventional pervaporation method has the disadvantages that the difference in molecular weight and boiling point, such as water, ammonia, and amines, is small, and it is not possible to separate substances with similar properties. It was necessary to solve the problem of separating water from an approximate substance such as ammonia while taking advantage of its simplicity and simplicity.

The present invention has been made by solving several problems as described above,
Claim 1, by pervaporation, a method for purifying water containing ammonia and / or amines as not neat, using a chitosan membrane as the permeable membrane, suppress permeation of ammonia and / or amines In addition, the present invention relates to a water purification method characterized by preferentially permeating water.
Claim 2 is, by pervaporation, a non neat a method for purifying water containing ammonia, sparse on a surface of an aqueous porous membrane regenerated cellulose film side of the composite membrane as a laminate of regenerated cellulose membrane supplying the water to a method for purifying water, characterized in that of preferentially transmitting ammonia suppresses the permeation of water using the composite membrane as the permeable membrane.
Claim 3 is, by pervaporation, a method for purifying water containing ammonia and / or amines as not neat, using chitosan films suppress permeation of ammonia and / or amines as a transparent film In addition, the present invention relates to a method for purifying water, wherein ammonia and / or amines permeated through the permeable membrane are adsorbed and removed using inorganic porous particles.
According to claim 4 pervaporation, a method for purifying water containing ammonia as not neat, the water regenerated cellulose film side of the sparse and the surface of the water film is laminated regenerated cellulose film composite membrane supplied, the composite film ammonia used as a transparent film preferentially transmits, methods purification of water, characterized in that the transparent over-film ammonia was not transmitted through the adsorbing removed using inorganic porous granules About.
Claim 5, by pervaporation, a method for purifying water containing ammonia as not neat, the water regenerated cellulose film side of the composite membrane as a laminate of regenerated cellulose film on the surface of the hydrophobicity film supplies, the the ammonia using the composite membrane as the permeable membrane is preferentially transmitted, said composite membrane fractions not passed through the transmittance of ammonia further performed pervaporation using chitosan film The present invention relates to a method for purifying water, wherein ammonia is permeated preferentially and ammonia that permeates through the chitosan film is adsorbed and removed using inorganic porous particles.
Claim 6 is the water purification method according to claim 3, wherein the inorganic porous particles adsorbing ammonia and / or amine impurities are heated to 100 to 200 ° C. under a reduced pressure of 10 Pa or less. The present invention relates to a water purification method characterized by desorbing an adsorbate of ammonia and / or amines.
Claim 7 is the method for purifying water according to claim 4 or 5, wherein the ammonia is adsorbed by heating to 100 to 200 ° C in a state where the inorganic porous particles adsorbing ammonia are decompressed to 10 Pa or less. The present invention relates to a method for purifying water.
Claim 8 is the continuous water purification device containing ammonia as an impurity, the continuous purification device consists pervaporation device and two or more impurity adsorption device, permeable membrane chitosan membrane of the pervaporation apparatus The impurity adsorbing device is provided with a regenerating device comprising heating means and pressure reducing means, and the permeation side of the pervaporation device is connected to an air supply pipe branched via a direction control valve. The above-mentioned impurity adsorbing device is connected to each branch end of the water.
Claim 9 is the continuous water purification device containing ammonia as an impurity, the said continuous purification device and the first and second pervaporation apparatus consists of two or more impurity adsorption device, said first par The permeation membrane of the evaporation apparatus is composed of a composite membrane in which a regenerated cellulose membrane is laminated on the surface of a hydrophobic membrane, and the regenerated cellulose membrane of the composite membrane is installed on the water supply side, and the second pervaporation permeable membrane configuration device consists chitosan film, the supply side of the supply side and said second pervaporation device of the first pervaporation device, passes through the permeable membrane of the first pervaporation device coupled to never been fractions through the second liquid feed pipe for feeding into the supply side of the pervaporation apparatus, reproducing apparatus pixel in the impurity adsorption apparatus comprising a heating means and the pressure reducing means Each is provided, on the permeate side of said second pervaporation apparatus is connected is air pipe diverged via the directional control valve, the impurity adsorption apparatus people to feed the branch end of the trachea husband is connected The present invention relates to a continuous water purification apparatus.

  In the invention according to claim 1, in order to preferentially permeate ammonia and amines, it is possible to purify water in which ammonia or amines, which have been considered impossible in the past, are dissolved as impurities by a pervaporation method. it can. This pervaporation method does not require conditions involving danger such as pressurization, and the decompression conditions required by the pervaporation method can be easily obtained in space. Moreover, since the apparatus can be miniaturized, it can be applied to water regeneration treatment under conditions such as the space environment.

Purifying invention according to claim 2, to suppress the permeation of water, in order to transmit the ammonia preferentially, conventional in ammonia which has been considered impossible is dissolved as an impurity water by pervaporation can do. This pervaporation method does not require conditions involving danger such as pressurization, and the decompression conditions required by the pervaporation method can be easily obtained in space. Moreover, since the apparatus can be miniaturized, it can be applied to water regeneration treatment under conditions such as the space environment.

  Since the invention according to claim 3 and claim 4 is a water purification method comprising a pervaporation method and inorganic porous particles, impurities dissolved in water can be removed with an extremely high removal rate. Moreover, this method does not require conditions involving danger such as pressurization, and the decompression conditions required in the pervaporation method can be easily obtained in space. Moreover, since the apparatus can be miniaturized, it can be applied to water regeneration treatment under conditions such as the space environment.

Since the invention according to claim 5 uses the pervaporation method using two different permeable membranes, impurities flowing into the inorganic porous particles can be reduced, and the inorganic porous particles are not regenerated. It can be used for a long time.
The invention according to claim 6, in the purification method of the water according to claim 3, in order to reproduce the inorganic porous particles, each adsorption capability has dropped, it is possible to a continuous treatment child water. In addition, since the inorganic porous particles are always decompressed in a normal case, the inorganic porous particles can be regenerated only by heating.
According to a seventh aspect of the present invention, in the water purification method according to the fourth or fifth aspect, the water can be continuously treated in order to regenerate the inorganic porous particles having a reduced adsorption capacity. In addition, since the inorganic porous particles are always decompressed in a normal case, the inorganic porous particles can be regenerated only by heating.

  The invention according to claims 7 and 8 can provide an apparatus capable of continuously purifying water. In addition, this apparatus does not use chemical means such as a solvent for the regeneration treatment of the inorganic porous particles, and can be suitably used in a limited environment such as a space environment.

First, a method for regenerating inorganic porous particles will be described.
The method for regenerating inorganic porous particles is to remove the adsorbate from the inorganic porous particles that have been used for adsorption removal of impurities such as ammonia and amines and have a reduced adsorption capacity using a physical method. How to play. Specifically, it is performed by heating the inorganic porous particles to be regenerated in a reduced pressure state. The decompression means is not particularly limited, and a vacuum pump or the like can be exemplified on the ground, and in a spacecraft or the like, it can be easily obtained by utilizing an ultrahigh vacuum space environment. Moreover, although a heating means is not specifically limited, Electric heating or infrared heating etc. can be illustrated.

The pressure reducing condition is a pressure of 10 Pa or less. This is because the adsorbate cannot be desorbed at a pressure higher than 10 Pa. However, unlike the space environment where an ultra-high vacuum of 10 ⁵ Pa can be easily obtained with an infinite displacement, a large facility is required to reduce the pressure to a pressure lower than 0.1 Pa on the ground. Is not preferable. Moreover, heating conditions shall be 100-200 degreeC. This is because the adsorbate cannot be desorbed at a temperature lower than 100 ° C., and even when heated to a temperature higher than 200 ° C., no further effect can be expected, and a larger facility is required. This is because neither case is preferable.

Under the conditions as described above , the adsorbate of ammonia or amines adsorbed on the inorganic porous particles can be almost completely desorbed by treatment usually for 3 to 10 hours. This regeneration method uses only physical means such as reduced pressure / high vacuum and heating without using any chemical means like the method using a solvent which has been conventionally performed as a regeneration method of inorganic porous particles. Inorganic porous particles can be regenerated. For this reason, post-treatment such as the solvent used for the regeneration treatment is not required, and it can be preferably used as a method for regenerating the inorganic porous particles in a limited environment such as a space environment. Furthermore, this regeneration method can be used to regenerate all kinds of inorganic porous particles such as activated carbon, charcoal, zeolite, palm culite, silica gel, activated alumina, titanium oxide, bentonite, acid clay, diatomaceous earth, magnesium oxide, and calcium carbonate. It can be suitably used.

Next, the water purification method by the pervaporation method according to the present invention will be described.
The water purification method described below is suitable for purification of water in which ammonia or amines are dissolved as impurities. First, the first water purification method will be described. Purification method of the first water by pervaporation, by electrical repulsion between the impurity and the permeable membrane, such as ammonia and amines dissolved in water, it is possible to suppress the permeation of impurities ammonia and amines, water the preferentially permeates, is the concentration of impurities in ammonia and amines on the permeate side (secondary side) a method for reducing compared to the supply side (primary side).

A chitosan membrane is used as the permeable membrane used in this water purification method. This is because the cationic groups with ammonia and amines chitosan film is electrically repel, since the transmission of the impurities of ammonia and amines can be suppressed.

The pervaporation method using this chitosan membrane as a permeable membrane can suppress the permeation of impurities such as ammonia and amines and can permeate water preferentially. The pressure difference between the supply side and the permeation side at this time is not particularly limited, but the supply side is set to atmospheric pressure or a pressure near atmospheric pressure, or the atmospheric pressure inside the spacecraft, and the pressure on the permeation side is the vapor pressure of the component that permeates the permeation membrane. It is preferable to keep it below. Examples of a method for keeping the permeation side below the vapor pressure include a method of reducing the pressure using a vacuum pump or the like, a method of supplying a gaseous substance that does not react with the permeation component to the permeation side, and the like. A method of reducing the pressure using is preferred. Also,
In a space environment such as a spacecraft, a decompression device such as a vacuum pump is not required, and therefore can be easily applied. Moreover, the temperature at the time of performing the separation is not particularly limited, but may be 20 to 90 ° C.

Next, the 2nd water purification method by the pervaporation method is demonstrated. Purifying method of the second water by pervaporation using a hydrophobic porous membrane composite film obtained by laminating a regenerated cellulose film on the surface of the water less polar compared with the slightly higher ammonia hydrophobic by transparent preferentially, a method for reducing the concentration of ammonia in the feed side.

Examples of the hydrophobic porous film used in this method include a polypropylene film, a polyethylene film, a silicon film, and a Teflon (registered trademark) film, but are not particularly limited .

The method for laminating the regenerated cellulose membrane on the surface of the hydrophobic porous membrane is not particularly limited. As the method, an acetone solution of cellulose acetate is coated on the surface of the hydrophobic porous membrane , dried, and then hydroxylated. The target composite membrane can be obtained by deacetylation using an aqueous sodium solution.

Under the same conditions as purification method of the first water described above, by pervaporation using a composite membrane as described above, it is possible to reduce the concentration of ammonia. That is, ammonia dissolved in water, due to the slightly higher hydrophobicity lower polarity than water, passes through the composite membrane preferentially. For this, the concentration of ammonia on the permeate side is higher than the concentration of the supply side, it is possible to reduce the concentration of ammonia in the feed side.

In conventional pervaporation, such as water and ammonia and amines, the molecular weight is close, the similar material nature was thought to not be separated. However, the above-described first and second water purification methods can separate water from ammonia and amines. Since these two methods are pervaporation methods, conditions that involve danger such as pressurization are not required. Further, the decompression condition required in the pervaporation method can be obtained very easily in the space environment. That is, this method can be said to be a method that can be suitably used under conditions such as a space environment.

Next, ammonia or amine contained in water or water vapor is obtained by simultaneously performing the above-described first and second water purification methods by the pervaporation method and the adsorption and removal method using inorganic porous particles. A method for purifying water that can almost completely remove water will be described.

First, the 3rd water purification method is demonstrated. This third water purification method includes a pervaporation method using a chitosan membrane as a permeable membrane and an adsorption removal method using inorganic porous particles. In this method, water containing ammonia or amines as impurities is treated by a pervaporation method using a chitosan membrane as a permeable membrane, and then the fraction permeated through the permeable membrane is adsorbed using inorganic porous particles. Is the method.

The pervaporation method using a chitosan membrane as the permeable membrane is the same as the method described in the first water purification method, and the description thereof is omitted. In addition, the inorganic porous particles used for the adsorption treatment of the fraction that has passed through the permeable membrane are not particularly limited, and are activated carbon, charcoal, zeolite, palm curite, silica gel, activated alumina, titanium oxide, bentonite, acidic clay. And diatomaceous earth, magnesium oxide, calcium carbonate and the like.

  Inorganic porous particles can be used for adsorbing and removing impurities as they are without pretreatment. Metals and alkalis adsorbed on inorganic porous particles in advance using a dilute acidic aqueous solution such as dilute hydrochloric acid and dilute sulfuric acid. It is preferable to remove impurities such as inorganic salts. This is because more impurities contained in the water or water vapor can be adsorbed and removed by removing in advance the impurities adsorbed on the inorganic porous particles. Although the density | concentration of the dilute acidic aqueous solution used is not specifically limited, It is preferable to set it as 0.1-1N. This is because contaminants cannot be sufficiently removed at a concentration lower than 0.1N, and further effects cannot be expected at concentrations higher than 1N, which is not preferable in any case.

  The method for removing impurities is not particularly limited, and after the inorganic porous particles are immersed in a dilute acidic aqueous solution for 1 to 24 hours, the inorganic porous particles are washed with a large amount of pure water, or the inorganic porous particles Examples include a method in which a body is packed in a column or the like, a dilute acidic aqueous solution is flowed down to remove impurities, and then a large amount of pure water is flowed down to be washed.

Using inorganic porous particles prepared by the above-described method, ammonia or amine can be obtained by a known method, for example, a method in which a column is filled with inorganic porous particles and a component that has passed through the chitosan membrane is passed through the column. the class impurities can be adsorbed and removed. Normally, in the pervaporation method, the component that passes through the permeable membrane is in a gaseous state, and can be supplied to the inorganic porous particles as a gas. Moreover, after liquefying once, it is also possible to supply to an inorganic porous granule.

Since this method is a pervaporation method using a chitosan membrane , as described above, it is possible to suppress the permeation of impurities such as ammonia and amines and to permeate water preferentially. For this reason, the concentration of ammonia and amines on the permeate side (secondary side) is greatly reduced compared to the supply side (primary side). Furthermore, by performing an adsorption treatment on the permeate side (secondary side) fraction using an inorganic porous granule, it is possible to remove almost completely even impurities contained in a small amount in water. The configurations other than those described above are the same as the configurations in the respective methods described above, and description thereof will be omitted.

Next, a fourth water purification method will be described. The fourth water purification method includes a pervaporation method using a composite membrane in which a regenerated cellulose membrane is laminated on the surface of a hydrophobic porous membrane as a permeable membrane, and an adsorption removal method using inorganic porous particles. This method is the same method as method for purifying water the second water containing ammonia, i.e., pervaporation using a hydrophobic porous membrane composite film obtained by laminating a regenerated cellulose film on the surface of a permeable membrane In this method, the fraction that has not been permeated through the permeable membrane after being treated by the method is adsorbed using an inorganic porous granule. In other words, this method is due to the use pervaporation method using a composite film obtained by laminating a regenerated cellulose film on the surface of the hydrophobic porous membrane as a permeable membrane, ammonia is transmitted preferentially. For this purpose, the concentration of ammonia in the supply side (primary side) is significantly reduced compared to the concentration of ammonia on the permeate side (secondary side). Furthermore, by performing an adsorption treatment of the fraction on the supply side (primary side) using inorganic porous particles, it is possible to remove almost completely even ammonia contained in a small amount in water. The configurations other than those described above are the same as the configurations in the respective methods described above, and description thereof will be omitted.

Next, a fifth water purification method will be described. The fifth water purification method consists of a pervaporation method using a chitosan membrane as a permeable membrane, a pervaporation method using a composite membrane in which a regenerated cellulose membrane is laminated on the surface of a hydrophobic porous membrane, and an inorganic porous particle. It consists of the adsorption removal method using. This method, use water containing ammonia as an impurity, the same method as method for purifying First the first water, i.e., the hydrophobic porous film composite film obtained by laminating a regenerated cellulose film on the surface of a permeable membrane The first pervaporation method was used. Next, the fraction that has not permeated the permeable membrane is treated by the same method as the second water purification method, that is, the second pervaporation method using a chitosan membrane as the permeable membrane.
Finally, it is a method in which a fraction that has passed through a permeable membrane made of a chitosan membrane is subjected to an adsorption treatment using inorganic porous particles. In other words, this method first the water containing ammonia for processing by the first pervaporation method using a composite film obtained by laminating a regenerated cellulose film on the surface of the hydrophobic porous membrane, preferentially a ammonia Can penetrate. For this, the concentration of ammonia in the supply side (primary side) is reduced compared to the concentration of ammonia on the permeate side (secondary side).
Further, the fraction on the supply side (primary side) is treated by a pervaporation method using a chitosan membrane as a permeable membrane. Wherein the described manner the second pervaporation suppresses permeation of ammonia, to the water can transmit preferentially, the ammonia was not removed in the first pervaporation Can be removed. Finally, the fraction permeated through the permeable membrane by the second pervaporation method is adsorbed using inorganic porous particles, so that even the ammonia contained in a small amount can be removed almost completely. It becomes possible. Since this method performs pervaporation twice using different permeable membranes, the amount of impurities adsorbed on the inorganic porous particles can be reduced. For this reason, the inorganic porous particles are used for a long time. be able to. The configurations other than those described above are the same as the configurations in the respective methods described above, and the description thereof is omitted.

Third described above, the fourth, the purification method of the fifth respective water can be substantially complete removal of impurities ammonia and amines dissolved in water. For this reason, it can use suitably as purification methods, such as various wastewaters, such as domestic wastewater, and urine, such as people and animals. In addition, each water purification method does not require conditions involving danger such as pressurization, and the pressure reduction conditions in the pervaporation method can be easily obtained in the space environment. The method can also be suitably used as a method for purifying water in a space environment. In addition, although the above three water purification methods have been described in detail as the water purification method by the adsorption removal method and the pervaporation method described above, other methods, for example, an adsorption removal method using inorganic porous particles It is also possible to use a method of separating the membrane by a pervaporation method after adsorbing and removing by the above method.

Furthermore, in the third, fourth, and fifth water purification methods, a continuous water purification method can be provided by using the above-described method for regenerating inorganic porous particles. Hereinafter, the continuous water purification method will be described. The continuous water purification method is the above-described third, fourth, and fifth water purification methods. When the adsorption removal ability of the inorganic porous particles is reduced or immediately before the decrease, the inorganic porous particles are used. Is heated in a state of high vacuum / reduced pressure to regenerate the inorganic porous particles and continuously purify the water. Conventionally, when the amount of adsorbed inorganic porous particles is reduced, it is necessary to temporarily stop the impurity removal operation and replace the inorganic porous particles. In contrast, in this method, the by using the process for regeneration of inorganic porous granules described, it is not necessary to replace the inorganic porous granules, continuously removing impurities ammonia and amines contained in the water can do. Third and foregoing description, in the fourth, fifth purification method for each water, after both surface-treated with a peroxide base over path translation method, the fraction having passed through the permeable membrane to process the inorganic porous granules It is configured. Usually, the permeation side (secondary side) of the permeable membrane is mostly depressurized, and unless special means are provided, the adsorption treatment operation with the inorganic porous particles is also performed under reduced pressure. That is, in each of the third, fourth, and fifth water purification methods described above, the inorganic porous particles are always in a reduced pressure state. For this reason, the inorganic porous particles are regenerated only by heat treatment. be able to. Other configurations are the same as the configurations in the respective methods described above, and the description thereof is omitted.

  Next, a continuous water purification apparatus used in the above-described continuous water purification method will be described with reference to the drawings. In addition, regarding the following continuous water purification apparatuses, the liquid supply pipe is a pipe through which liquid flows, and the air supply pipe is a pipe through which gas flows.

First, the continuous water purification apparatus according to the first embodiment of the present invention will be described. FIG. 1 is a schematic view showing a continuous purification apparatus according to the first embodiment of the present invention. The continuous water purification device (1) according to the first embodiment shown in FIG. 1 includes a pervaporation device (2), two impurity adsorption devices (3), and a regeneration device provided in each impurity adsorption device. Consists of. A chitosan membrane is used as the permeable membrane (201) in the pervaporation device (2) of the continuous water purification device (1) according to the first embodiment of the present invention. This is because the chitosan film can suppress the permeation of ammonia and amines as described above .

  As the impurity adsorption device (3) of the continuous water purification device (1) according to the first embodiment of the present invention, a known device equipped with an adsorbent such as an inorganic porous particle can be used. Examples of the inorganic porous particles include activated carbon, silica gel, activated alumina, palm curite, charcoal, and zeolite, but are not particularly limited. In the continuous water purification device (1) according to the present invention, at least two impurity adsorption devices (3) are required, and three or more impurity adsorption devices (3) can be provided. This is because, in order to continuously purify the water, the adsorbent of one adsorbing device is subjected to regeneration treatment while the other adsorbing device is used to adsorb and remove impurities. In the illustrated continuous water purification device (1), two impurity adsorption devices are provided. Each of the impurity adsorption devices (3) is provided with a regeneration device. This regeneration device is provided with a heating means (4) and a decompression means (not shown), and is regenerated by heating the adsorbent in a decompressed state. The decompression means and the heating means are not particularly limited, and the decompression means can be exemplified by a space high vacuum environment itself in space, a vacuum pump or the like on the ground, and the heating means (4) as infrared heating, Examples thereof include electric heating. The decompression condition is a pressure of 10 Pa or less, and the heating condition is 100 to 200 ° C. In the continuous water purification device (1) of the illustrated example, the pressure reducing means constituting the regenerating device is provided via the air supply pipe (52).

  In the continuous water purification device (1) according to the first embodiment of the present invention, the permeation side (secondary side) (202) of the pervaporation device (2) and the supply side of each adsorption device (3) ( The primary side is connected via an air supply pipe (53) provided with a direction control valve (61). The supply side (primary side) (203) of the pervaporation apparatus (2) is connected to a liquid supply means (not shown) via a liquid supply pipe (54). Moreover, the permeation | transmission side (secondary side) of each impurity adsorption | suction apparatus (3) is provided with the air supply pipe (51) and the air supply pipe (52) provided with the direction control valve (62). The air pipe (51) is connected to a purified water recovery device (not shown) and a decompression means (not shown). The decompression means connected to the air supply pipe (51) is provided to decompress the permeation side (secondary side) (202) of the pervaporation device (2). The air pipe (52) is connected to a decompression means (not shown) that constitutes the above-described regenerating apparatus. These decompression means can be exemplified by a vacuum pump or the like on the ground, or an ultra-high vacuum space in a space environment such as a spacecraft, but is not particularly limited. Further, the purified water recovery device (not shown) is not particularly limited, and examples thereof include a cold trap that can cool water vapor and recover it as ice or water. The fraction that did not permeate the permeable membrane (201) of the pervaporation device (2) was connected to the liquid feeding means (not shown) via the liquid feeding tube (55), and again the pervaporation device ( If necessary, it may be configured to be fed through a filtration filter through the liquid feeding pipe (54).

  Next, a method for continuously purifying water using the continuous water purification apparatus according to the first embodiment of the present invention will be described. First, water is supplied to the supply side (primary side) (203) of the pervaporation apparatus (2) through the liquid supply pipe (54) using a liquid supply means (not shown). Since the permeation membrane (201) used in this pervaporation device (2) preferentially passes water, the permeation side (secondary side) (202) of the pervaporation device (2) is composed of ammonia and amine. It becomes a fraction (water vapor) in which the amount is reduced. This fraction (water vapor) is supplied to one impurity adsorbing device (lower adsorbing device in the illustrated example) through the air supply pipe (53), and the impurities contained in the water vapor are adsorbed and removed. The water vapor from which impurities have been removed by passing through the impurity adsorption device (3) is supplied to the purified water recovery device through the air pipe (51), and the purified ice or water is recovered by cooling the water vapor here. .

  When the adsorption capacity of one impurity adsorption device (lower adsorption device in the illustrated example) decreases, the fraction transmitted through the permeable membrane (21) of the pervaporation device (2) by the direction control valve (61). Is supplied to the other impurity adsorbing device (the upper adsorbing device in the illustrated example). Further, by switching a direction control valve (62) provided in the air supply pipe on the secondary side of the impurity adsorption device, the other impurity adsorption device is connected to the air supply tube (52), and one impurity adsorption device is connected to the air supply tube ( 51). In one impurity adsorption device (3), the adsorbent is regenerated by heating the adsorbent with the heating means (4). The regenerated adsorbent can exhibit the original adsorption capacity again. By switching the direction control valve, water can be continuously purified.

Next, the continuous water purification apparatus according to the second embodiment of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing a continuous water purification device (1) according to the second embodiment of the present invention. The continuous water purification device (1) according to the second embodiment of the present invention includes a first pervaporation device (204), a second pervaporation device (208), and two or more impurity adsorption devices ( 3). As the permeable membrane (206) of the first pervaporation device (204), a composite membrane in which a regenerated cellulose membrane is laminated on the surface of a hydrophobic porous membrane is used. Such composite membranes, suppresses the permeation of water can be selectively permeable to ammonia. Examples of the hydrophobic porous film include a polypropylene film, a silicon film, and a Teflon (registered trademark) film, but are not particularly limited . Also, a method of laminating a surface regenerated cellulose membrane of the hydrophobic porous film is not particularly limited, as the method is to coat the acetone solution of cellulose acetate on the surface of the hydrophobic porous membrane, after drying, Examples thereof include a method for obtaining a desired composite membrane by deacetylation using an aqueous sodium hydroxide solution. In addition, the supply side (207) of the 1st pervaporation apparatus (204) is provided with the liquid feeding means (not shown) via the liquid feeding pipe (54).

A chitosan membrane is used as the permeable membrane (210) of the second pervaporation device (208). Chitosan film is to suppress permeation of impurities ammonia and amines, water can be transmitted preferentially.

  In the continuous water purification device (1) according to the second embodiment, at least two impurity adsorption devices (3) are required as in the first embodiment, and it is possible to provide three or more. This is because, in order to continuously purify water, the adsorption removal of impurities is performed using the other impurity adsorption device while the adsorbent of one impurity adsorption device is regenerated. In the continuous water purification device (1) according to the second embodiment of the illustrated example, two impurity adsorption devices (3) are provided. Each of the impurity adsorption devices (3) is provided with a regeneration device. This regeneration device is provided with a heating means (4) and a decompression means (not shown), and is regenerated by heating the adsorbent in a decompressed state. The decompression means (not shown) and the heating means (4) are not particularly limited, and the decompression means (not shown) may be a vacuum pump or the like on the ground, or in a space environment such as a spacecraft, A vacuum space environment can be illustrated, and examples of the heating means (4) include infrared heating and heating wire heating. In addition, in the continuous water purification apparatus (1) according to the second embodiment of the illustrated example, the pressure reducing means (not shown) constituting the regenerating apparatus is provided via the air supply pipe (52).

  In the continuous purification device (1) of the second embodiment of the present invention, the supply side (primary side) (207) of the first pervaporation device (204) and the supply of the second pervaporation device (208). The side (primary side) (211) is connected by the liquid feeding pipe (57), and the fraction that has not permeated the permeable membrane (206) of the first pervaporation device (204) is the second pervaporation device. It is configured to be supplied to the supply side (primary side) (211) of (208). In addition, the permeation | transmission side (secondary side) (205) of a 1st pervaporation apparatus (204) is provided with the pressure reduction means (not shown) through the air feed pipe (56). This decompression means is provided to decompress the permeation side (secondary side) (205) of the first pervaporation device (204), and examples of the decompression means include a space environment and a vacuum pump. There is no particular limitation. The impurity adsorption device (3) is connected via an air supply pipe (53) provided with a direction control valve (61) on the transmission side (secondary side) (209) of the second pervaporation device (208). The Further, a pressure reducing means (not shown) and a purified water recovery device are provided through a gas supply pipe (51) provided with a direction control valve (62) on the permeation side (secondary side) of each impurity adsorption device (3). (Not shown) is provided. This decompression means (not shown) is provided to decompress the secondary side (209) of the permeable membrane (210) of the second pervaporation device (208). Etc., but is not particularly limited. Further, the purified water recovery apparatus is not particularly limited, and examples thereof include a cold trap that can cool water vapor and recover it as water.

Next, a method for continuously purifying water using the continuous water purification device (1) according to the second embodiment of the present invention will be described. First, water is supplied to the supply side (primary side) (207) of the first pervaporation apparatus (204) through the liquid supply pipe (54) using a liquid supply means (not shown). Permeable membrane used in the first pervaporation device (204) (206) suppresses the permeation of water, in order to transmit the ammonia preferentially, the supply side of the first pervaporation apparatus (204) the concentration of ammonia in the (primary side) (207) decreases. Next, the fraction on the supply side (primary side) (207) of the first pervaporation device (204) is fed to the supply side (primary side) (211) of the second pervaporation device (208). Feed through tube (57). Second permeable membrane for use in pervaporation device (208) (210), in order to preferentially permeate water to suppress the passage of ammonia, transmission of the second pervaporation apparatus (208) side (secondary side) (209) is the fraction ammonia is reduced becomes (water vapor). This fraction (water vapor) is supplied to one impurity adsorbing device (lower impurity adsorbing device in the illustrated example) through the air supply pipe (53) to adsorb and remove impurities contained in the water vapor. The water vapor from which impurities have been removed by passing through the impurity adsorption device is supplied to a purified water recovery device (not shown) through an air supply pipe (51), where the purified ice or water is recovered by cooling the water vapor. Is done. The fraction that did not pass through the permeable membrane (210) of the second pervaporation apparatus (208) was connected to the liquid feeding means via the liquid feeding pipe (58), and again the first pervaporation. It is good also as a structure supplied to an apparatus (204).

  When the adsorption capacity of one impurity adsorption device (lower impurity adsorption device in the illustrated example) decreases, the adsorbent of one impurity adsorption device is regenerated by the same method as described in the first embodiment. In addition, impurities can be removed by adsorption in the other impurity adsorption apparatus. The continuous water purification apparatus according to the second embodiment of the present invention is provided with two different pervaporation apparatuses, and these two apparatuses can remove considerable impurities. It can be maintained for a long time.

  In the continuous water purification apparatus according to the present invention described above, an impurity adsorption device is provided on the permeation side (secondary side) of the permeable membrane. In a normal case, the permeation side (secondary side) of the permeable membrane is always in a reduced pressure state, and the impurity adsorption device provided on the permeation side (secondary side) of the permeable membrane performs the adsorption process in a reduced pressure state. That is, when the adsorbent is regenerated, the regeneration process can be performed only by heating.

  The present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples.

(Example 1: Adsorption removal of ammonia in water)
A deodorant for refrigerator (trade name: Non-Sumell, manufactured by Hakugen Co., Ltd.) with reduced adsorptive capacity is taken into a desorption container, and the pressure is reduced to 10 Pa with a vacuum pump. Regeneration treatment was performed by heating to ° C. Next, 0.086% aqueous ammonia was added at 5 ml / min. To a column (30 mmΦ × 300 mm) packed with 60 g of the regenerated deodorizer for refrigerator. The ammonia concentration of a predetermined amount of discharge liquid was measured.
The ammonia concentration was measured using ion chromatography under the following conditions. In the examples described later, the measurement was performed under the same conditions. Analytical column: Shinmpack IC-C-3 (4.60 mm Φ × 10 cm), moving bed: 1.0 / min., Temperature: 40 ° C., detection: electric conductivity detector (TOYOSODA C0-8000).

(Example 2: Adsorption removal of ammonia in water)
A column (30 mmΦ × 300 mm) of 50 g of a deodorizer for refrigerator (trade name: Non-Sumeru, manufactured by Shiramoto Co., Ltd.), which was regenerated twice, was packed in 0.07% aqueous ammonia at 5 ml / min. The ammonia concentration of a predetermined amount of discharge liquid was measured. The reproduction process was performed in the same manner as in Example 1 above.

(Example 3: Adsorption removal of ammonia in water)
The charcoal (trade name: MC-450, manufactured by Date Forest Association) with reduced adsorptive capacity was heated at about 170 ° C. for 5 hours in a state where the pressure was reduced to 10 Pa using a vacuum pump, and a regeneration treatment was performed.
36 g of this charcoal was packed in a column (30 mmΦ × 300 mm) and 0.1% aqueous ammonia was added at 5 ml / min. The ammonia concentration of a predetermined amount of discharge liquid was measured.

(Example 4: Adsorption removal of ammonia in water)
The refrigerator deodorizer (trade name: Non-Sumeru, manufactured by Shiramoto Co., Ltd.) with reduced adsorptive capacity was regenerated by the same method as shown in Example 1. A column (30 mmΦ × 300 mm) was packed with 60 g of the regenerated deodorizer for refrigerator, and 0.1% ammonia water was added at 5 ml / min. The ammonia concentration of a predetermined amount of discharge liquid was measured.

(Example 5: Adsorption removal of ammonia in water)
Silica gel with reduced adsorption capacity (silica gel white, 5-10 mesh, manufactured by Junsei Chemical Co., Ltd.) is placed in a desorption container, depressurized to 10 Pa with a vacuum pump, and heated to about 170 ° C. with an electric heater or infrared heater in this state. The reproduction process was performed. 100 g of this silica gel was packed in a column (30 mmΦ × 300 mm) and 0.097% aqueous ammonia was added at 5 ml / min. The ammonia concentration of a predetermined amount of discharge liquid was measured.

(Example 6: Ammonia adsorption removal in water)
Adsorbent is obtained by immersing 200 g of silica gel (silica gel white, 5-10 mesh, manufactured by Junsei Chemical Co., Ltd.) in 500 ml of 1N hydrochloric acid at room temperature for 24 hours, and then repeatedly washing with 500 ml of pure water 5-10 times. The metal ions inside were removed. This washed silica gel was subjected to adsorption removal, and the silica gel with reduced adsorption ability was regenerated by the same method as in Example 5 above. The same test as in Example 5 was performed using 100 g of this silica gel.

(Example 7: Adsorption removal of ammonia in water)
The silica gel used in Example 6 and having reduced adsorptive capacity was regenerated by the same method as in Example 5. The same test as in Example 5 was performed using 100 g of this silica gel.

(Example 8: Adsorption removal of ammonia in water)
The silica gel used in Example 7 and having reduced adsorptive capacity was regenerated by the same method as in Example 5. The same test as in Example 5 was performed using 100 g of this silica gel.

  The results of Examples 1-8 are shown in Table 1.

  As shown in Table 1, it can be seen that the regeneration treatment method using both heating and decompression of the inorganic porous particles having reduced adsorption ability can recover the adsorption ability of the inorganic porous particles.

(Examples 9 to 13)
A 1% chitosan solution was prepared by dissolving 10 parts by weight of chitosan having a deacetylation degree of 98% (CTA020213, manufactured by Katakura Chikkarin) in a mixed solution of 980 parts by weight of water and 10 parts by weight of acetic acid. 140 g of this 1% chitosan solution was cast on an acrylic resin plate (20 cm × 20 cm × 1 cm thickness). It left still horizontally and the solvent was dried and removed, and the chitosan acetate film | membrane was formed on the acrylic resin board. By immersing the chitosan acetate membrane in a 1% sodium hydroxide aqueous solution, the chitosan membrane is regenerated, and after removing sodium hydroxide using a large amount of pure water, it is attached to an acrylic plate and dried. A dry chitosan film having a thickness of 30 μm was obtained. This chitosan membrane was attached to a pervaporation permeation cell, and about 0.1% aqueous ammonia solution (refer to the table for actual measured values) was fed to the supply side by a roller pump. The permeation side was connected to a vacuum line, the pressure was reduced to 1 × 10 to 1 × 10 ² Pa, and pervaporation was performed at the permeation temperature shown in Table 2 below. The permeate was condensed and collected in a trap cooled with liquid nitrogen. The collected permeation component was analyzed by high performance liquid chromatography, and ammonia was quantified. As the high performance liquid chromatography column used, Shimpack IC-C3 was used, and ammonia was detected using an electric conductivity detector.

  The results of Examples 9 to 13 are shown in Table 2.

As shown in Table 2, since the pervaporation method uses a chitosan membrane as a permeable membrane, ammonia dissolved in water can be removed.

(Examples 14 to 20)
The chitosan membrane used in Example 9 was attached to a pervaporation permeation cell, and about 0.1% of the aqueous ammonia solution was fed to the supply side by a roller pump on the supply side (see the table for actual measurement values). A column filled with 10 g of silica gel (12 mmΦ × 100 mm) was connected to the permeate side, and the outlet of this column was connected to a vacuum line equipped with a trap cooled with liquid nitrogen and a vacuum pump, and 1 × 10 to 1 × 10 ^2. The pressure was reduced to Pa, and pervaporation was performed at a permeation temperature of 30 to 50 ° C. The permeate was condensed and collected in a trap cooled with liquid nitrogen. The collected permeated component ammonia was quantified.

  The results of Examples 14 to 20 are shown in Table 3.

As shown in Table 3, the water purification method uses a pervaporation method using a chitosan membrane as a permeable membrane and an adsorption removal method using inorganic porous particles, so that ammonia dissolved in water is almost completely removed. Can be removed.

(Examples 21 to 31)
The chitosan membrane used in Example 9 was attached to a pervaporation permeation cell, and about 0.1% aqueous ammonia solution (refer to the table for actual measured values) was fed to the supply side by a roller pump. A trap in which two columns (12 mmΦ × 100 mm) packed with 10 g of silica gel on the permeate side were connected in series (Examples 21 to 26) or in parallel (Examples 27 to 31), and the outlet of this column was cooled with liquid nitrogen And a vacuum line equipped with a vacuum pump, the pressure was reduced to 1 × 10 to 1 × 10 ² Pa, and pervaporation was performed at a permeation temperature of 30 to 50 ° C. The permeate was condensed and collected in a trap cooled with liquid nitrogen. The collected permeated component ammonia was quantified.

(Example 32)
The chitosan membrane used in Example 9 was attached to a pervaporation permeation cell, and about 0.1% aqueous ammonia solution (refer to the table for actual measured values) was fed to the supply side by a roller pump. Two columns (12 mmΦ × 100 mm) packed with 10 g of spherical activated carbon (trade name: X7100, LotNo. DXW01) are connected in parallel on the permeate side, and a trap cooled by liquid nitrogen and a vacuum pump are installed. The pervaporation was performed under the condition of a permeation temperature of 50 ° C. under reduced pressure of 1 × 10 to 1 × 10 ² Pa. The permeate was condensed and collected in a trap cooled with liquid nitrogen. The collected permeated component ammonia was quantified.

  The results of Examples 21 to 26 are shown in Table 4, and the results of Examples 27 to 32 are shown in Table 5.

As shown in Tables 4 and 5, the pervaporation method using a chitosan membrane as a permeable membrane and the water purification method using a plurality of inorganic porous particles, so that ammonia dissolved in water is almost completely removed. can do.

(Example 33)
The chitosan membrane used in Example 9 was attached to a pervaporation permeation cell, and about 0.1% ethylenediamine aqueous solution (refer to the table for actual measured values) was fed to the supply side by a roller pump. The permeation side was connected to a vacuum line, the pressure was reduced to 1 × 10 to 1 × 10 ² Pa, and pervaporation was performed at the permeation temperatures shown in Table 6 below. The permeate was condensed and collected in a trap cooled with liquid nitrogen. The collected permeated ethylenediamine was quantified.

(Examples 34 to 35)
A column in which the chitosan membrane used in Example 9 was attached to a pervaporation permeation cell and packed with silica gel (Example 34) or spherical activated carbon (trade name: X7100, LotNo. DXW01) (Example 35) on the supply side ( The outlet of this column was connected to a vacuum line equipped with a trap cooled with liquid nitrogen and a vacuum pump. About 0.1% ethylenediamine aqueous solution (refer to the table for measured values) is supplied to the supply side with a roller pump, and the pressure is reduced to 1 × 10 to 1 × 10 ² Pa, and the permeation temperature is 30 to 50 ° C. Pervaporation was performed. The permeate was condensed and collected in a trap cooled with liquid nitrogen. The collected permeated ethylenediamine was quantified.

  The results of Examples 33 to 35 are shown in Table 6.

As shown in the results of Table 6, since it is a perpaper method using a chitosan membrane as a permeable membrane, amines such as ethylenediamine dissolved in water can be removed.

(Examples 36 to 38)
The outer surface of a porous hollow fiber membrane (EX540VS-12, manufactured by Mitsubishi Rayon) is coated with a 10% cellulose acetate / acetone solution, air-dried, deacetylated with 1N aqueous sodium hydroxide solution, and the regenerated cellulose membrane is made porous A composite hollow fiber membrane was obtained by forming on the surface of a porous hollow fiber membrane. This composite hollow fiber membrane was fixed to an acrylic resin module. This composite hollow fiber membrane was mounted on a pervaporation apparatus, and a liquid containing ammonia was supplied to the outside of the composite hollow fiber membrane. A tube-type pump was used for feeding the supply liquid, and the liquid was fed at a rate of 188 ml (40 ° C.) to 194 ml (60 ° C.) per minute. The supply liquid and the heat exchanger were immersed in the same constant temperature layer, and the temperature of the supply liquid to the module was monitored at the inlet and the outlet. Both ends of the inner side of the composite hollow fiber membrane were connected to a vacuum line, and the permeation component was collected by a test tube trap cooled with liquid nitrogen. The pressure during the permeation test was measured with a Pirani gauge, and was performed at 30 to 40 Pa. The ammonia concentration of the fraction that permeated through the permeable membrane and the fraction that did not permeate were measured. Further, as a comparative example, a test similar to the above was performed using a commercially available hollow fiber module (trade name: CLILLANCE E hollow fiber type dialyzer, manufactured by Terumo Corporation).

  The results of Examples 36 to 38 are shown in Table 7.

As shown in Table 7, since it is a pervaporation method using a permeable membrane made of a composite membrane in which a regenerated cellulose membrane is laminated on the surface of a hydrophobic membrane, water permeation is suppressed and ammonia is preferentially permeated. be able to. Moreover, a commercially available hollow fiber module could not separate water and ammonia.

It is a schematic diagram of the continuous water purification apparatus which concerns on 1st embodiment of this invention. It is a schematic diagram of the continuous water purification apparatus which concerns on 2nd embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 .... Continuous water purifier 2 ... Pervaporation device 201 ... Permeation membrane 204 ... First pervaporation device 208 ... Second pervaporation device 210 ... Permeation membrane 3 ... Impurity adsorption device 4 ... Heating means 53 ... Air supply pipe 61 ... Direction control valve

Claims (9)

By pervaporation, a method for purifying water containing ammonia and / or amines as not neat, using a chitosan membrane as the permeable membrane, preferentially a water suppresses the permeation of ammonia and / or amines Water purification method characterized by making it permeate | transmit. By pervaporation, a method for purifying water containing ammonia as not neat, and supplies the water to the regenerated cellulose film side of the hydrophobicity porous film composite membranes in a laminate of regenerated cellulose film surface , purification method of water, characterized in that the ammonia is preferentially transmitted suppresses the permeation of water using the composite membrane as the permeable membrane. By pervaporation, with ammonia and / or a method for purifying water containing amines, to suppress the permeation of ammonia and / or amines with chitosan membrane as the permeable membrane as a non neat, translucent filtration membrane A method for purifying water, wherein ammonia and / or amines that permeate the water are adsorbed and removed using inorganic porous particles. By pervaporation, a method for purifying water containing ammonia as not neat, and supplies the water to the regenerated cellulose film side of the sparse and the surface of the water film is laminated regenerated cellulose film composite membrane, wherein the ammonia using the composite film as a transparent film preferentially not transmit the purification method of the water, characterized in that the transparent over-film ammonia was not transmitted through the adsorbing removed using inorganic porous granules. By pervaporation, a method for purifying water containing ammonia as not neat, and supplies the water to the regenerated cellulose film side of the sparse and the surface of the water film is laminated regenerated cellulose film composite membrane, wherein the ammonia using the composite membrane as the permeable membrane is preferentially transmitted, a fraction not permeated through the composite membrane, suppresses permeation of ammonia further performed pervaporation using a chitosan membrane water Is preferentially permeated, and ammonia permeated through the chitosan film is adsorbed and removed using inorganic porous particles. The method for purifying water according to claim 3, wherein the inorganic porous particles adsorbing ammonia and / or amine impurities are heated to 100 to 200 ° C under a reduced pressure of 10 Pa or less, and ammonia and / or amine. A method for purifying water, characterized by desorbing adsorbates of a kind. The water purification method according to claim 4 or 5, wherein the inorganic porous particles adsorbed with ammonia are heated to 100 to 200 ° C under a reduced pressure of 10 Pa or less to desorb ammonia. Purification method. A continuous water purification device including ammonia and / or amines as not neat, the continuous purification device consists pervaporation device and two or more impurity adsorption device, permeable membrane Chitosan of the pervaporation apparatus The impurity adsorbing device is provided with a regeneration device comprising heating means and decompression means, and a permeation side of the pervaporation device is connected to an air supply pipe branched via a direction control valve. A continuous water purification apparatus , wherein the impurity adsorption device is connected to each branch end of the trachea . A continuous water purification device containing ammonia as an impurity, the said continuous purification device and the first and second pervaporation apparatus consists of two or more impurity adsorption apparatus, transmission of the first pervaporation device The membrane is composed of a composite membrane in which a regenerated cellulose membrane is laminated on the surface of a hydrophobic membrane, and the regenerated cellulose membrane of the composite membrane is installed on the water supply side, and the permeable membrane of the second pervaporation device consists chitosan film includes a supply side of the supply side and said second pervaporation device of the first pervaporation device, a fraction not permeated through the permeable membrane of the first pervaporation device second is connected via a liquid feed pipe for feeding into the supply side of the pervaporation apparatus, reproduction apparatus are each provided, et al comprising a heating means and the pressure reducing means in the impurity adsorption device And characterized in that the permeate side of said second pervaporation apparatus is connected is air pipe diverged via the directional control valve, the impurity adsorption apparatus to people feed each branch end of the trachea is connected Continuous water purification device.

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