Description
ADSOliPTION STRUCTURE, ADSORI'TION MODULE, AND
METHOD FOR PRODUCING SAME
Technical field
[OOO 11
The present invention relates to a pre-treatment technique for a reverse osmosis
membrane that separates and removes water-dissolved organic matter and electrolytes used for
5 high pcrformancc treatment in a water treatment process such as waste water reclamation and
ocean water desalinization.
Backgro~rnd art
[0002]
Reverse osmosis membranes arc used in high performance treatment of water
10 purification. Semipermeable membranes are used for reverse ostnosis membrane surfaces and
materials for the setnipermeable membranes are roughly classified into cellulose acetate-based
and aromatic polyamide-based matcl.ials. Aromatic polyamide-based reverse osmosis
membranes have high water permeability and high electrolyte filtering performance, and are
therefore widely used for industrial applications. As for structures thereof, a mt~lti-layered
15 semipermeable membrane structure with an aromatic polyatnide membrane formed on a
foraminulous support body is ofen used and a film tliick~iesso ftlie aromatic polyamide portion
is 1 1.1m or less.
1:OOO3]
Reverse osmosis membranes are used to remove water-dissolved organic matter
20 or electrolytes for ocean water desalinization, manuficturing of pure water used for
~nanofacturing of semiconductor or other precision clcctronic apparatuses, lligh performance
treat~ilento f clean water and final treatment of'sewagc/wastc water or the like.
[OOOS]
When a reverse osmosis membrane is used for final treatment of sewage among
25 such applications, water is generally supplied to the reverse osmosis membrane through the
following treatment processes. First, coarse contaminants and garbage or the like contained in
sewage are removed through a sieve called "screen." Next, fine suspended materials such as
sand are settled and separated in a settling reservoir by adding a coagulant as required.
Supernatant water still contains suspended solids and dissolved organic matter or the like, and
these are decomposed using microorganisms. Metabolites of the niicroorganisms are produced
as sludge, and sludge and water are separated through settlement in the settling reservoir or by
passing the sludge and water through a precision membrane filter. Primary treated sewage
6 water treated in this way contains substantially no suspended solids, and is subjected to
disinfection or the like in this stage, discharged into rivers or purified to quality of water that can
be reused depending on application such as tree planting spray water. In Japan, primary treated
sewage water is discharged into rivers in this stage and circulated by taking advantage of natural
purification. Iiowever, in the Middle East, inland areas in a continent, islands without rivers or
10 tlie like, there are few rivers, lakes and marshes necessary and sufficient for natural purification,
and therefore there is a growing demand for further purifying primary treated sewage water and
reusing it as drinking water or industrial water. Reverse osmosis membranes are used to
remove dissolved organic matter or electrolytes in the primary treated sewage water in this final
treatment.
15 [OOOS]
The primary treated sewage water contains electrolytes accounting for 1% or less,
dissolved organic matter equivalent to 3 to 20 mg/L ofTOC (total organic carbon) though these
figures may change depe~idingo n treatment or the like up to thc preceding stagc. Wlicn thcsc
elements are separated using the reverse osmosis membrane, it is possiblc to reduce the
20 electrolytes to 1 ppln or less, and tlie dissolved organic matter to 1 mg/lL or less.
[0006]
The reverse osmosis membrane used for final sewage treatment is oAen folded
into a shape called "spiral" in order to increase tlie surface arca of the membrane within a
module. The bag-shaped reverse osmosis membrane is fixed to a corc part in thc ccntcr, wound
25 up like an umbrella and accom~ilodated in a cylinder. Cylindrical modules having a diameter of
4 irtches or 8 inches and a length of I m are the mainstream.
100071
'l'he reverse osmosis mcmbrane is a kind of separation tiicmbrane and there are
two schemes of water filtering using a separation membrane. One is a dead-end filtration
30 scheme which is a scheme whereby a full amount of water supplied is allowcd to pass through a
film and components unable to pass through tlie film are deposited on the surface of the film.
The other is a cross-flow.filtration scheme whereby water flows parallel to the surface of the
film, part of the water passes through the film as filtered water and the remainder, when
dissolved matter thereof reaches a high concentration, is taken out of the module as condensed
water. The latter cross-flow filtration scheme is used for filtering with the reverse oslnosis
membrane. This scheme reduces precipitation of dissolved matter onto the fill11 surface and an
increase of operation load due to an incrcase in concentration. Howevel; even the cross-flow
filtration scheme involves a problem that dissolved solids are adsorbed onto the film surface and
5 the amount of filtered water deteriorates over time.
[0008]
Examples of adsorptive materials onto the film surface include scale which is an
electrolyte that is precipitated when a concentration thereof in the vicinity of the film surface
becotnes high, bio-fouling that lnicroorganisms in water propagate thetnselves on the film
10 surface, and organism fouling that organic matter is adsorbed. Clean water is periodically
poured onto the film surface and adsorptive materials are removed by a shearing force, but when
organic matter is adsorbed, the adsorptive materials cannot be completely removed by the
shearing force, and the adsorptive materials gradually accumulate and a water transtnission rate
deteriorates. Power (pressure) is increased to secure a constant trans~nission rate, which may
15 however lead to an increase in the electric power cost of the pump. Furthermore, a cleaning
fluid causes the reverse oslnosis membrane to gradually deteriorate, and thus an ion rejection rate
decreases. When the deterioration advances, the reverse os~nosism embrane {nodulen eeds to
be replaced. When the reverse osrnosis inemhrane tnodule is replaced, operation has to be
stopped for rnany hours, and moreover since the reverse osrnosis membrane module cannot bc
20 recycled, it should bc replaced by a new reverse osrnosis lnctiibratie module, which lnay rcsult in
a decrease in capacity utilization, an increase in costs ofconsumables of the reverse osmosis
membrane, an increase in running cost per unit quantity of water such as waste treatment cost.
Prior art docurnetits
Patent documents
25 100091
I'atent document 1 : 51'-132-38648 17
Patent document 2: JP-A-2005-111407
I'atent document 3: JP-A-2008-136919
Brief description of the invention
30 Probleln to be solved by the invention
[OO 1 01
Therefore, there is a method for adding a pre-treatment process of removing
organic matter before a reverse osmosis membrane in advance to thereby extend the life thereof
until the reverse osmosis membrane is replaced. Examples of the pre-treatment method include
a method of decomposing organic matter and a method of removing organic matter through
adsorption or coagulation, and the latter method that adsorbs organic matter is disclosed in Patent
6 document I as a method using an adsorptive material made of the same material as a reverse
osmosis membrane.
[OOl I ]
Activated carbon is generally used as an adsorptive material for organic mattel:
However, with the method using activated carbon, most of organic matter contained in primary
10 treated sewage water is adsorbed, and therefore activated carbon soon reaches adsorption
saturation and activated carbon has to be replaced more frequently, and even i f the reverse
osmosis membrane is replaced less frequently, its cost benefit is poor.
100 121
An adsorptive material is required to have a structure that allows a sufficient
15 permeate flow rate to be obtained when primary treated sewage water is passed therethrough.
On the other hand, securing a large surface area that contacts water is essential for efficient
adsorption. As a method of increasing the s~~rfaacree a, activated carbon is provided in forms
of powder, spalls, partic,les or the like, but when such activated carbon is used in watel; since a
water channel beco~nesn arrower, a sulf cient flow rate is hardly achieved. Adsorptive
20 materials other than activated carbon, when tiicy arc granular, may cause sirnilar problems.
Furthermore, activated carbon contains pores for expanding the surface area, but substances
trapped in the pores can hardly be eliminated and recovery of adsorption perfbrmance by means
of cleaning is practically impossible.
[00 131
25 When water treatment is performed using a reverse osmosis membrane, I'atent
document 2 discloses a method using an adsorptive material to remove organic matter dissolved
in water. 'The adsorptive material, liowevet; docs not providc a suficicnl sorlkcc itroil, resulting
in a problcm that a largc amount ol'adsorptivc matcrial is necessary.
[OO 1 41
30 When the reverse osmosis membrane is contaminated and affected by clogging,
the pressure (power) must be increased to secure a constant transmission rate, which leads to an
increase in the power cost of the pump. Furthennore, although the reverse osmosis membrane
is cleaned to remove contamination, chemicals cause the reverse osmosis membrane to gradually
deteriorate and ion rejection decreases. I f this condition worsens, the reverse osmosis
5
membrane has to be replaced. On the occasion of replacement ofthe reverse os~nosis
membrane, operation needs to be suspended for a long time, making it difficult to supply
rccycled water stably. In sewage reclamation in particular, the water supplied to the reverse
osmosis inembrane contains a large quantity of organic lnatter and clogging with dissolved
5 organic matter constitutes a considerable proble~n.
LOO1 51
There are two major mechanisms of clogging of the reverse ostnosis ~nernbrane
caused by dissolved organic matter. The first one is that organic matter is adsorbed onto the
surface of the reverse osmosis membrane, clogging the film surface or molecular level pores and
10 deteriorating film pcrformancc. The second one is largely concerned with a reverse osmosis
mcmbranc module and caused when dissolved organic rnatler re~nainsu ndissolved and deposited
on the film surface or between the film and a spacet; thus clogging the channel. The second
clogging mechanism caused by the nodule structure in particular occurs on tlie entrance side of
the module and the permeate flow rate decreases at the back of the module even when the film
15 does not deteriorate. As a conventional method of removing dissolved organic matter, Patent
docun~ent 1 discloses a method using an adsorptive material made ofthe same material as a
reverse osmosis membrane. Further~noreI, 'atent docu~nen2t discloses a method using fiblaus
high polymer and porous ceramic to increase the contact area between treated water and the
reverse os~nosisin ernbrane.
20 [OOl GI
When sewage is treated using a reverse os~nosis~ ne~nbranaeft er treating
organism activated sludge in a sewage recla~nation process, refractory organic matter dissolved
in watcr is adsorbed onto the surface of thc reversc os~nosism embrane, and watcr per~neability
deteriorates over time, causing a proble~n with a stable supply ofpermeable water. 'fhe
25 performance ofthe deteriorated revcrse ostnosis membrane may be recovered by cleaning the
surface tl~ereofwitlci lean water, but it is difficultt o recover the full function and the clcaning
liquid causes thc film to degrade and causes tlie quality of permeable water to dcgradc. For this
reason, when the deterioration advances to a certain degree, the reverse osmosis ~nembrancn ccds
to be replaced. When the life of the reverse ostnosis membrane is short, the water treatment
30 running cost increases. Since the amount oforganism contained in water supplied to the
reverse osmosis membrane is particularly large, the water treatment running cost constitutes a
considerable problem.
[00 1 71
There is a method of removing organic matter in a pre-treatment process, but it is
6
difficult to obtain the effect at low cost. This is because a large volume of adsorptive material
is necessary and reuse ofthe adsorptive material is difficult.
[00 1 81
It is an ob,ject of the present invention to solve the above-described problems, add
5 a low-cost pre-treatment process, thereby extend the life of a reverse osmosis mernbra~iea nd
reduce the running cost incurred in recla~nation of sewage or waste water.
Means for solving the problem
[00 191
For solving the above problenis, the invention provides, for example, an
lo adsorption structure for adsorbing organic matter in a water to be treated, comprising: an outer
wall, a plurality of flow paths arranged at an inside of the outer wall, and a partition wall
separating the flow paths from each other, characterized in that the partition wall includes
communication holes which have dianieters less than diameters of the flow paths, and form
communications between the flow paths and includes an adsorption material for adsorbing the
15 organic matter.
Advantageous Effccts of lnvention
[OO2O]
The present invcntion adds a low cost pre-treatment process, extends the life of a
reversc osmosis membrane, and can thereby reduce the running cost incurred in recla~nationo f
20 sewage.
Brief I>escription of Drawings
1002 1 ]
[Fig. I ] Fig. 1 is a water treatment flow diagram using an adsorption module.
[Fig. 21 Fig. 2 is a schematic diagram showing a structure of the adsorption nodule when
25 assembled.
[Fig. 31 Fig. 3 is a schematic diagram of'a ceramic honeycomb structure viewcd from a treated
water supply direction.
[Fig. 41 Fig. 4 is a schematic side view of the ceramic honeycomb structure.
[Fig. 51 Fig. 5 is an example of a cross-sectional view of the ceramic honeycomb structure.
30 [Fig. 61 Fig. 6 is a molecular structure of an adsorptive material according to an embodiment of
the present invention.
Modes for carrying out the invention
[0022]
I-lereinafler, an embodi~nenot f the present invention will be described with
reference to thc accornpanyi~igd rawings.
5 Embodiment 1
[0023]
Fig. I shows water treatment equipment according to an embodiment of the
present invention. The water treatment equiprnent is provided with an adsorption module 1, a
water storage lank 5, a water supply pump 6 arid a reverse osmosis membrane module 4.
10 100241
In an embodiment according to the present invention, primary treated sewage
water supplied to the adsorption module 1 is water to which a series of treatment has been
applied such as treatment of removing dust or the like using a screen, treatrnent ofcausing fine
suspended materials such as sand to settle out and to be removed by adding a coagulant thereto,
15 and treatment of decomposing organic rnatter using microorganisms. The prirnary treated
sewage water contains salt and dissolved organic matter. The primary treated sewage water
treated in this way contained dissolved organic rnatter equivalent to 2.48 mgll., ofTOC (total
organic carbon).
100251
20 The present invention passes the primary treated sewage water through the
adsorption module 1 and passes the water through thc reverse osrnosis membrane 3 while
pressurizing the water using the water supply pump 6, and call tlicreby relllovc organic matter
and salt in the treated water, co~npletingw ater reclamation. Thc primary treated sewagc water
is treated while passing through the ceramic honeycomb structure 2 where a high polynier
25 inaterial is modified in the adsorption module 1 and stored in the water storage tank 5. 'l'he
water is supplied to the reverse os~llosism cmbrane 3 from the water storage tank 5 by the water
supply p~unp6 .
[0026]
First, proble~nsa nd solutions will be described concerning a case where
30 ~nicroorganisrnt reatment is performed in sewage recla~nationa nd then treated in the reverse
osmosis membrane module 4, but the reverse os~nosism embrane is also effective in removing
water-dissolved organic matter in other applications such as ocean water desalinization,
manufacturing of pure water used for manufacturing of semiconductor or other precision
electronic apparatuses, high perfor~nancet reatment of clean water and reclamation of
sewagelwaste water (including a case where microorganis~n treatment is not used ill
combi~iation).
[0027]
5 The primary treated sewage water supplied to the reverse osmosis lnelnbrane in
sewage reclamation is water after organic rnatter decolnposition treatment by microorganistns
and contains refractory organic matter equivalent to 3 to 20 lndL of TOC (total organic carbon).
The number oftypes of the refractory organic matter is not specified to one. In a cross-flow
filtration scheme, eolnponents separated by the reverse ostnosis membrane are discharged
10 together with condensed water, and therefore dischargeable organic matter is not a cause for
deterioration of the reverse osrnosis membrane, and thus need not be removed actively. The
present invention solves the problem using an adsorptive material in a pre-treatment process that
selectively and efficiently adsorbs and retnoves only organic tnatter adsorbed onto the surface of
the reverse os~nosism embrane according to the water treatment flow shown in Fig. I .
15 Adopting such an adsorptive material makes it possible to reduce the amount of adsorptive
material and realize low cost pre-treatment.
[0028]
First, the organic matter adsorbed onto the surface of the reverse osmosis
~ilenibranew as analyzed. Since Inany components are contained, tllc components eo~lldn ot be
20 specified, but it was confirmed that organic matter containing carbonyl groups or carboxyl
groups was easily adsorbable. In addition, components containing amino groups and siloxane
and the like containing Si are also included in coliiponents to be adsorbed.
[0029]
Fullhermore, when the amount of refractory organic matter adsorbed to the
25 reverse os~nosism embrane was examined, it was determined that the refPactory organic lnatter
dissolved into water adsorbed to the reverse os~nosism embrane was equivalent to on the order of
5% of'l'OC and the rest of organic matter was not adsorhcd to the reverse os~nosisin etnhrane
even if it cxisted in watcr and would not cause water permeability to deteriorate.
[00301
30 It is said that there are roughly two mechanisms whereby a reverse osfnosis
membrane adsorbs organic matter. One is intermolecular interaction in which affinity acts
between materials having similar ~noleculars tructures. It is assumed froin an analysis of
adsorptive materials that since a material containing carbonyl groups, amino groups or the like
has high affinity with matter causing deterioration of the reverse osmosis membrane, a high
polymer that contains carbonyl groups or amino groups as a repetition unit is preferable.
Exa~nplesth ereof include polyamidc, polyimide, polyester, polycarbonatc, polyurethane, acrylic
resin, urea resin and polyethylene terephthalate. In order to realize an angle of contact of 40
degrees or more, a principal chain or a side chain tnay preferably contain carbon hydride or
6 aromatic. ring with four or Inore carbons, Furtherinore, for allinity with siloxane. and the like,
the principal chain or side chain preferably contains a siloxane structure. Furthermore, the
number of types ofthe structure included in the principal chain or side chain is not limited to
one, and adsorption efficiency may improve by including a plurality of structures.
[003 1 ]
10 When there is an adsorptive material in a pre-treatment process which has an
adsorption surface with adsorption performance equivalent to that of a reverse os~nosis
membrane surface, if it is brought into contact with another adsorptive material in a pretreatment
process having a surface area equal to or greater than the surface areaaf the reverse
os~nosistn etnbrane before being introduced into the reverse ostnosis membrane, it is possible to
15 remove organic matter that causes deterioration and double the life of the reverse ostnosis
membrane.
In order to increase the surface area ofthe adsorptive material, the shape of the
adsorptive material may be granular, mesh, fiber, filter or the like, but not limited to these.
LO0321
20 Particularly, in the case of porous rnedia such as filter, thc surface area is large.
If the surface area ofthe adsorptive material is large, it is possible to reduce the volu~neo f the
equipment to be added to the pre-treatment process or set the adsorptive material in a tank of the
existing equipment.
[0033]
26 This is used for a process of adsorbing and removing water-dissolved organic
matter for sewage reclamation, ocean water desalinization, ~nanufacturi~oigf pure water used for
~nanufacturingo f se~niconductoor r other precision electronic apparatuses, high perfortnance
treatment of clean water or the like.
[0034]
30 In such a water treatment process, it is possible to pass treated water containing
water-dissolved organic matter through a ceramic honeycomb structure having inany channels
partitioned by barriers and apply adsorption treatment thereto.
[0035]
The adsorption tnodule of the present embodiment will be described using
10
drawings. Fig. 2 is a side view of an example of the adsorption module 1 used for a sewage
treatment apparatus. The adsorption module 1 is assumed to be a structure provided with a
filter having a ceramic honcycornb structure (porous ceramic honeyco~nbs tructure 2). A
cera~nich oneycomb structure 2 that supports an adsorptive illaterial 13 such as polyanlide is
5 housed by a filte,r support body 8 in a housing 7 (acrylic. container) via a grasping membel: The
support body 8 may be made of such a material, have such a thickness and use such a holding
method that allows water to pass therethrough without resistance and provides such strength that
when water is passed therethrough at 0. I MPa, a position variation in the center of the
longitudinal axis with respect to the length in the longitudinal direction between fixed ends falls
10 within 5% and may be a material containing no substance eluted to water, and, for example, a
mesh spacer of polyethylene, polypropylene, polyethylene terephthalate, polystyrene or the like
as resin-based material, mesh of stainless steel, titanium or the like or punching metal as a metalbased
material may be used. In the present embodiment, a punching metal having a thickness
of 1 lnln was used as the support body 8.
15 [0036]
As shown in Figs. 3 to 5, the ceramic honeyco~nbs tructure 2 of the present
embodiment includes an outer wall 9, a plurality of channels 12 provided inside the outer wall 9,
barriers 10 that partition between the channels 12, and a high polymer material 13 provided for
the harriers 10. The channels 12 arc arrangcd in directions that. cross cach olhcr in their
20 longitudinal directions and arc formed by capping, with sealing, through holes that penetrate
from the influent side to the effluent side. To be Inore specific, the channel 12 includes a first
channel 12a where the influent side oftreated water is open and the opposite effluent side is
capped by a hole cap sealing I I and a second channel 12b where the effluent side ofthe treated
water is open and the opposite influent side is capped by the hole cap sealing 11. On the planes
25 that longitudinally cross each other, the first channel 12a and the second channel 12b are
alternately arranged both longitudinally and laterally. Furthermore, innu~nerable
communication holes (not shown) whose diameters are smaller than the channel diameter are
perforated in the outer walls 9 and the barriers 10 formed ofceramic honeycomb.
LO0371
30 As shown in Fig. 5, water before treatment flows into the ceramic structure 2 in
the adsorption module 4 through the first channel 12a which is open on the influent side. The
influent water before treatment flows into the second channel 12b through the fine
co~nmunicationh oles in the barriers 10. The high polymer material 13 as an adsorptive
material of organic matter is provided on the surface of the barriers 10 or on the top layer of the
surface of the fine co~nmunicationh oles in the barriers I0 and the high polymer material I3
adsorbs and removes organic matter in the water before treatment when the water before
treatment passes through the barriers.
The water before treatment that has flown into the second channel 12b flows out
5 from the effluent side of the ceramic structure 2 where the channel 12b is open.
[0038]
As shown in Figs. 3 to 5, the barriers 10 have a grip-like shape having a thickness
of 0.1 lnln to 1 mm. When the thickness of the barriers 10 is equal to or greater than 0.1 mm,
the strength and the shape of the barriers I0 can be secured easily. Furthermore, when the
10 thickness of the barriers 10 was less than I mm, the pressure necessary for the treated water to
pass therethrough was not excessive and was practical. Furthermore, the barriers 10 have a
feature of including fine communication holes having an average diameter of 0.005 mm to 0.05
mm. With the fine co~nmunicationh oles having an average diameter of0.005 lntn or greater,
the resistance of water passing therethrough does not increase, the amount of treated water can
15 be easily obtained and clogging with components other than the adsorption component is less
likely to occur. Furthermore, when the average hole diameter is less than 0.050 mtn, the effect
of surface area expansion by adopting the porous cera~nich oneycomb structure 2 is great and the
contribution ofthe pre-treatment process equipment to suppression of the volulne is
considerable.
20 1100391
Furthermore, the channel 12 has a rectangular shape, one side of which is 0.5 mtn
to 8 mtn. When one side ofthe channel 12 is 0.5 mm or greatel; the treated water containing
organic lliatter dissolved in water is less likely lo adsorb organic matter in the vicinity ofthe
entrance of the ceramic honeycomb structure 2, blocking the channel 12 in the vicinity of the
26 entrance, which rnakes it possible to effectively use the ceramic honeycomb structure 2 up to its
end at the back. On the other hand, when one side ofthe channel 12 is smaller than 8 mm, the
barriers 10 of the ceramic lloneycomb structure 2 can be thicker and sufficie~itm echanical
strength can be secured and the possibility that the ceramic honeyco~nbs tructure 2 may be
damaged when a pressure is applied to treated water may be reduced, which is desirable.
30 Furthermore, the shape of the channel 12 is not limited to the rectangular shape.
[0040]
At an end of the ceramic honeyco~nbs tructure 2, an end of a desired channel 12 is
capped with sealing and the channel 12 is shaped such that a hole cap sealing 11 is present at
either end. The water before treatment flows from the first channel 12a without the hole cap
12
sealing I 1 on the influent side in the channel 12, passes through the fine communication holes of
the barriers 10, and the barriers 10 can thereby reliably adsorb and treat organic matter dissolved
in treated water. The water before treatment that has passed through the barriers 10 passes
through the second channel 12b without the hole cap sealing 1 I on the effluent side and flows
6 out of the ceramic structure 2. The porous ceramic honeycomb structure 2 forms the hole cap
sealings 11 at positions away fro111 the end faces of many channels 12 partitioned by the porous
barriers 10 generated into a honeycomb shape. The same material as the porous ceramic
honeycomb structure 2, organic material, and material not dissolved in treated water such as
inorganic niaterial can be used for the hole cap sealing I 1 in the ceramic honeycomb structure 2.
10 The hole cap sealing 11 as a plug is pushed and fixed using a stick or syringe. Furlhennore, as
show11 in Figs. 3 to 5, when the hole cap sealings I I are alternately introduced onto the end faces
of the channel 12, it is possible to increase the number of barriers 10 that contact both the first
channel 12a and the second channel 12b, inside which the water before treatment passes through,
and thereby improve the efficiency.
16 [0041]
The porosity ofthe material used for the barriers 10 is preferably 45% to 70%.
When the porosity used for the barriers 10 is greater than 45%, the fine holes formed in the
barriers 10 are less likely to be clogged, hiling to serve as communication holes, and it is
thereby possible to secure a st~ficiennt umber of communication holes. Furthermore, when the
20 porosity used for the barriers 10 is less than 70%, it is possible to secure mechanical strength of
the barriers 10 and reduce the possibility that the barriers 10 may be damaged when a pressure is
applied to treated watei; which is therefore desirable.
[0042]
Moreover, the porosity of the material used fol. the hole cap sealing 1 I is
25 preferably s~nalletrh an the porosity of the material used h r t he barriers 10, namely 0% to 40%,
and the thickness of the hole cap sealing 11 is preferably greater than the thickness of the barriers
10. When the porosity of the niaterial used ibr the hole cap sealing 11 is less than 40%, the
possibility that treated water passing through the barriers I0 may pass through the hole cap
sealing 11 is lower; which is therefore desirable. Making the porosity of the material used for
30 the hole cap sealing 11 smaller than the porosity of the material used for the barriers 10 can
ensure that treated water passes through the barriers 10.
[00431
The material constituting the barriers 10 may preferably contain alumina or
alumina-containing multi-layered oxide. It was confirmed through an experiment that since
alumina groups were exposed from tlie surface, it was possible to adsorb part of dissolved
organic matter in treated water and decompose refractory dissolved organic matter of high
polymer into low molecules. In particulal; alumina or alumina-containing multi-layered oxide
contained in tlie material constituting tlie barriers 10 is preferably a material containing at least
5 one of aluminosilicate, sillicnanite, mullite, spinel, cordierite, aluniinum titanate, and lithium
aluminum silicate.
[0044]
Furthermore, similar effects can also be obtained by forming an aluminacontaining
coat on at least some or all of the surfaces ofthe barriers I0 or the fine
10 communication holes in the barriers 10.
LOO451
Furthermore, when undissolved in treated watel; the material constituting the
barriers 10 may be different fiom the material constituting the hole cap sealing 1 1 . Since the
material is used for water treatment and thus heat-resistance is not required, the material
15 constituting the hole cap sealing I 1 may contain at least one of glass, polyimide, polya~nide,
polyimide amide, polyorethane, acrylic. epoxy, polypropylene. and Teflon (registered
trademark). Thus, the temperature at which the hole cap sealing I I is formed may be lower
than the temperature at which the barriers 10 are formed.
LO0461
20 Furthermore, the material constituting the hole cap sealing I I may be a multilayered
material made up of ceramic particles and an organic high polymer material. Ceramic
particles used for the material constituting tlie hole cap sealing 11 may be preferably at least one
ofalumina, silica, magnesia, titania, zirconia, zircon, cordierite, spinel, aluminum titanate, and
lithium alurninuni silicate.
26 LO0471
The method of forming the hole cap sealing 11 ~ s eas p rinting mask having an
opening at a position corresponding to the channel 12 of the ceramic structure 2, and can thereby
apply paste to be used for the hole cap sealing 11 at a desired position of the channel 12 formed
by the barriers 10 using a screen printing method and form the hole cap sealing 11.
30 [0048]
Furthermore, the method of forming the hole cap sealing 11 uses a dispenser
having a plurality of nozzles arranged at a position corresponding to the channel 12 of the
ceramic structtlre 2, and can thereby apply paste to be used for the hole cap sealing 11 at a
desired position of the channel 12 formed by the barriers 10 using a paste discharging method
and form the hole cap sealing I I . For example, for high polymer application, an ultra-fine
needle with a micron-order needle point for medical use is used. First, the needle (nay be
inserted up to the vicinity ofthe sealing part and the needle may be pulled out while spraying the
high polymer.
5 [0049]
In order to prevent conta~ninationo fthe reverse os~nosism embrane 3 used for a
post-process of the adsorption module 1, the high polyiner material 13 is modified on the surface
of the barriers 10 of the porous ceramic honeycomb structure 2 used for the adsorption module 1
or the top layer of the surface of the fine communication holes in the barriers 10. The high
1.0 polymer inaterial 13 may be applied to any one of co~nbinationso f all or some of the barriers 10
of the porous ceramic honeycomb structure 2, the first-half and the last-half thereoC only the
inner walls of the barriers I0 of the first-half part, and only the inner walls of the of the barriers
I0 of the last-half part. As the high polymer material 13, it is effective to modify a material
including at least one type of high polymer containing two or more chetnically equivalent amino
15 groups with respect to a repeating unit. It has been confirmed through an experiment that the
high polylner material 13 has a feature of adsorbing organic matter that contaminates the reverse
osmosis membrane 3 used in the post-process of the adsorption module 1.
[0050]
The method of applying the high polymcr ~natcrial 13 lo the porous ceramic
20 honeyco~nbs tructure 2 is similar to sollie of the mctliods used to form the hole cap sealing I I,
and the high polymer material 13 which is an adsorptive material is applied and formed at a
desired position in the clia~~ne12l formcd by the barriers 10 using a dispenscr having a plurality
of nozzles arranged at a desired position according to a discharging method. I-'or example, an
ultra-fine needle with a micron-order needle point for medical use is used for high polymer
26 application. First, the needle may be inserted up to the vicinity of the end ofthe hole cap
sealing I I and thc ~icedlem ay be pulled out while spraying the high polymer. 'l'his is a method
whereby the high polymer material 13 that adsorbs and removes organic liiatter is applied to all
or some of the surfaces ofthe barriers I0 and the surfaces of inside holes of 0.005 to 0.050 lnln
to a degree ofthickness that will not fill the inner fine holes ofthe barriers 10, preferably I00 nm
30 or less, and in this case, water passes through the barriers 10 with substantially no resistance and
the applied high polymer material 13 adsorbs and relnoves water-dissolved organic matter.
coos I]
The mechanism in which the high polymer material 13 adsorbs water-dissolved
organic matter is affected by inter~nolecular interaction. It is preferable to use polymer
containing an -NI~I-b ond having high affinity with a carbonyl group, carboxyl group or arotnatic
ring as thc high poly~nerm aterial 13 for adsorption based on an analysis of adsorbed organic
matter. Exa~npleso f inclusion of an -NI-1- bond in the repeating unit of polytner include
polyatnide, polyi~nide, polyurethane, urea resin, polypeptide (protein), polyethyleneimine,
6 polybenzimidazole, and polybenzoxazole. Materials containing an -Nl-I- bond in a side chain or
principal chain !nay also be used as other materials. Fig. 6 shows a chemical structure of the
high polymer. Exa~nplesth ereof include polyallylamine and polyvinylamine. Furthermore,
materials containing a carbonyl group and siloxane structure in the principal chain or side chain
may also be used for affinity with an -NH- bond or siloxane and the like. Furthennore, the
10 structure included in the principal chain or side chain is not limited to one type, and inclusion of
a plurality of structures makes it possible to adsorb a wide range of types of ~nixturesc ontained
in water and improve the adsorption eficiency.
[0052]
Polyamide and cellulose acetate in general use may be used as the adsorption high
I5 polytner material 13, but the adsorption high poly~nerm aterial 13 is not limited to these.
f00531
Furthennore, a photocatalyst may be supported for the porous ceramic
honeyco~nbs tructure 2 or high polymer material 13 to decon~poseo rgti~~mica tter. As the
photocatalyst, titanium oxide, strontiu~nti tanate, zinc oxide, iron oxide, tungsten oxide or the
20 like may be used but the photocatalyst is not limited to these.
[00541
By performing purification treatlnellt on water before trcalrne~lut sing the porous
ceramic honeyco~nbs tructure 2 ~nodifiedw ith the adsorption high polymer material 13, it is
possible to efficiently reinove organic matter with a large surface area, and since the channel 12
26 of the adsorption module I is wide, clogging is less likely to occur and it is possible to reduce the
frequency of cleaning the reverse oslnosis membrane 3 in thc post-process of the adsorption
nodule 1 and reduce the running cost.
[0055]
By performing the pre-treatment process of the revcrsc os~nosism embrane 3
30 using such an adsorptive material 13, it is possible to selectively adsorb only organic matter
which is the cause of performance deterioration of the reverse osmosis membrane 3 beforehand
and remove the organic matter froin within the water, and since the amount of organic matter
accu~nulatedin the adsorptive material 13 is small, the adsorptive material 13 is replaced less
frequently, and a low cost pre-treatment method can be obtained by limiting the adsorption
f~~nctioton the outerniost surface.
Embodiment 2
[0056]
I-lereinafter, a method of ~nanufactl~rinthge ceramic structure 2 will be described.
5 [0057]
'The ceramic honeycomb structure 2 in which the adsorptive material 13 is
supported is manufactured as follows. Powder of kaolin, talc, silica, alumina or the like is
prepared, powder of cordierite-based raw materials is prepared so as to have a mass ratio of
SOz: 48 to 52%, A1203: 33 to 37%, and MgO: 12 to 15%, a binder such as methyl cellulose,
10 hydroxy propylinethyl cellulose, and a lubricant are added to this, sufficiently mixed in a dry
process, with a specified quantity of water added, sufficiently kneaded to create a plasticized
ceramic raw material. Next, the raw material is extrusion-molded using a metal die for
extrusion molding, cut and dried to create a dry body having a honeyco~nbs tructure. Next, the
outer perimeter of the dry body is worked and removed, and since the channel 12 located at the
15 outerniost perimeter has no barriers 10 between itself and the outside, the dry body having a
honeycomb structure has a concave groove which is open and extends outward in the axial
direction. Furthennore, as a typical cxamplc, aflcr being sintered at 1400°C, a coat containing
cordierite particles and colloidal silica is applied to the channel 12 which is open and extends
outward, and sintered to create a cordierite-based ceramic honeycomb structure 2 in which Inany
20 channels 12 having a rectangular cross section partitioned by the barriers 10 are formed inside
the outer wall 9.
l:005 X]
Since the ceramic honeycomb structure 2 is manufactured by changing the
thickness ofthe barriers I0 to 0.05 niln to 2.0 mm, various metal dies for extrusion molding werc
25 prcpared and made as prototypes. When the thickness of the barriers 10 was greater than 0.1
mm, the strength of the barriers I0 was s~~fficieanntd it was easy to keep the shape. On the
other hand, when the thickness of the barriers 10 was smaller than 1.0 mm, it was not necessary
to apply any excessive pressure to make treated water pass therethrough, which was practical.
Thus, it was confirmed that the thickness of the barriers LO is preferably 0.1 tnln to 1.0 mm.
30 [0059]
Furthermore, for the barriers 10, the ceramic honeycomb structure 2 with fine
communication holes having an average diameter of 0.003 mm to 0.1 mm was manufactured.
In the case of co~nrnunicationh oles having an average diameter of0.005 mm or greater, the
resistance when water passes therethrough was s~nalal nd a suficient amount of treated water
was obtained. Furthermore, no clogging is caused by components other than adsorption
co~nponents. On the other hand, when the average hole diameter is less than 0.050 mm, the
effect of expansion of the surface area by adopting the porous ceramic honeycomb structure 2 is
6 considerable, which contributes to suppression of the volume of the pre-treatment process
equipment.
[0060]
Furthermore, the channel 12 was manufactured into a rectangular shape, with
each side having a length of 0.3 rntn to 10 mm. In the case ofthe channel 12 with each side
10 having a length of 0.5 lnln or greater, treated water containing water-dissolved organic matter
adsorbs organic matter in the vicinity of the entrance of the ceramic honeycomb structure 2,
hardly blocks the channel 12 in the vicinity of the entrance and allows the ceramic honeycomb
str~lctl~2re t o be effectively used up to the end at the back. On the other hand, when the length
of each side of the channel 12 is smaller than 8 mm, the barriers 10 ofthe ceramic honeycomb
15 structure 2 can be thicker, have sufficient mechanical strength and are less susceptible to damage
when a pressure is applied to the treated water using the pump 6.
LO06 1 ]
The ccramic honeycomb structure 2 was prepared by changing the composition
and sintering temperature so that the porosity of the material to be used for the barriers 10
20 became 30% to 85%. When the porosity of the material to be used for the barriers 10 is greater
than 45%, fine holes formed in the barriers 10 are likely to become communication holes,
making it possible to effectively use the holes. Furthermore, a suficient amount of
communication hole can be secured and no excessive pressure is required to allow treated water
to pass therethroogh. On the other hand, when the porosity of the material to be uscd for the
26 barriers 10 is less than 70%, it is possible to secure suficient mechanical strength of the barriers
10 and the ceramic honeycomb structure 2 is assumed to be less susceptible to damage when a
pressure is applied to the treated water using the pump 6.
LO0621
Furthermore, the porosity of the material used for the hole cap sealing I 1 was also
30 prepared by changing the composition and sintering temperature. When the porosity ofthe
material used for the hole cap sealing 11 exceeds 40%, part of the treated water passing through
the barriers 10 passed through the hole cap sealing 11. Therefore, the porosity of the material
used for the hole cap sealing 11 is smaller than the porosity of the material used for the barriers
10, preferably 0% to 40%, and by making the thickness of the hole cap sealing I 1 in the channel
longitudinal direction greater than the thickness of the barriers 10, treated water could reliably
pass through the barriers 10. Thus, by making the material used for the hole cap sealing 1 1
have a s~nallerp orosity than that of the material used for the barriers 10, it was possible to ensure
that treated water passed through thc barricrs 10.
5 100631
Thus, in the present invention, as an example of the structure of the cerarnic
honeycolnb structure 2, the adsorption module 1 was prepared using one having an outside
diameter (diameter) of 5.66 inches, a total length of 6 inches, with the barriers I0 having a
thickness of 0.32 mm, a pitch of 1.57 inm, and an initial pressure loss of0.85 mnAq (at 7.5
1.0 ~m'lmin).
[0064]
Patent document 3 shows an example of the method of manufacturing such a
ceramic honeycomb structure 2.
This Patent document relates to a method of manufacturing the ceramic
16 honeycomb structure 2 for cleaning particulates contained in an exhaust gas of a diesel engine.
Embodiment 3
100651
Another exa~npleo f the method ofmanufacturi~lgth c ccramic honeycomb
20 structure 2 will be described. The present e~nbodi~nelisl ts imilar to Embodiment 2 in the
method of manufacturing the ceramic honeycomb but different in the method of manufacturing
the hole cap scaling 1 1 .
[0066]
As the material used fbr the hole cap sealing I I, slurry was prepared by causing
26 the composition of the ceramic honeycomb structure 2 to contain a solvent and an effective
arnount of the slurry was discharged for sealing at predetermined alternate positions on the
entrance side and the exit side ofthe channel 12 of the cetamic honeycomb structure 2 using a
dispenser having a plurality of nozzles arranged at desired positions. Afier that, the slurry was
dried and sintered to preparc the holc cap scaling 11.
30 [0067]
Furthermore, in addition to the dispenser, a screen printing method can be used to
form the hole cap sealing 11. When using the screen printing method, a printing mask having
an opening at a predetermined position was aligned with a predetermined position of the ceramic
honeycolnb structure 2 and slurry of high viscosity was discharged through the opening of the
printing mask. Then, the slurry was dried and sintered to prepare the hole cap scaling I I . An
excellent hole cap sealing I 1 could be made as in the case of using the dispenser.
[0068]
Furthermore, the porosity of material used for the hole cap sealing 11 was also
5 prepared by changing the composition and the sintering temperature. When the porosity of the
material used for the hole cap sealing 1 1 exceeds 40%, part of the treated water passing through
the barriers I0 passed through the hole cap sealing 11. Therefore, the porosity of the material
used for the hole cap sealing 1 I is smaller than the porosity of the material used for the barriers
10, needs to be 0% to 40%, and by making the thickness of the hole cap sealing 11 greater than
10 the thickness of the barriers 10, treated water could reliably pass through the barriers 10. Thus,
by making the material used for the hole cap sealing 11 have a smaller porosity than that ofthe
material used for the barriers 10, it was possible to ensure that treated water passed through the
barriers 10.
[0069]
15 In the ceramic honeycomb structure 2, a material which is not dissolved in treated
water such as the same material as the porous ceramic honeycomb structure 2, organic material
or inorganic material could be used for some hole cap sealings 11 and the plugs were pushed in
and fixed using a stick or syringe. Furthem~orea, s shown in Figs. 3 to 5, a sealant was
introduced alternately into the end faces of the channel 12 so as to havc a structrrre in which
20 water could pass through the barriers 10.
[00701
Thus, as an example ofihc structure ofthe ceramic honeycomb structure 2 ofthe
present invention, one having an outside diameter (diameter) of 5.66 inches, a total length of 6
inches, with the barriers 10 having a thickness of 0.32 mm, a pitch of 1.57 mm, and an initial
26 pressure loss of 0.85 11nnAq (at 7.5 ~ ~ n ~ l mcoiunld) be prepared.
Embodiment 4
1007 I]
The ceramic honeycomb structure 2 was prepared using the salne method as (hat
of Embodiment 2 or the like except applying contents shown below.
30 [0072]
As the material constituting the barriers 10, a material containing alumina or
alumina-containing multi-layered oxide was used. It was confirmed through an expcrirnent that
since alumina groups were exposed from the surface, it was possible to adsorb part of dissolved
organic matter in treated water and decompose refractory dissolved organic matter of high
polymer into low ~llolecules. In particular, a good result was obtained when at least one of
aluminosilicate, sillimanite, mullite, spinel, cordierite, aluminum titanate, and lithium aluminum
silicate was used as alumina or alumina-containing multi-laycred oxide to be contained in the
6 material constituting the barriers 10.
[0073]
Furthermore, similar effects could also be obtained by forming an aluminacontaining
coat on at least some or all of the surfaces of the barriers 10 or the fine
comtnunication holes in the barriers 10.
10 (00741
Furthermore, different materials were used for the barriers 10 and for the hole cap
sealing I I . I-lowever, these materials are undissolved in treated water. Since the material is
used for water treatment and thus heat-resistance is not required, the material constituting the
hole cap sealing I1 may contain at least one ofglass, polyimide, polyamide, polyimide amide,
15 polyurethane, acrylic, epoxy, polypropylene, and Teflon.
100751
Furthermore, a multi-layered material made up of ceramic particles and an
organic high polymer material were also used as the material constituting the hole cap sealing I I .
At least one of alumina, silica, magnesia, titania, zirconia, zircon, cordieritc, spinel, aluminu~n
20 titanate, and lithium aluminum silicate was used as ceramic particles used for the material
constituting the hole cap sealing 11.
[0076]
At least one of polyimide, polyamide, polyimide amide, polyurethane, acrylic,
epoxy, polypropylene, and Teflon was used as thc organic high polymer material constituting the
25 hole cap sealing 1 I .
[0077]
When the organic high polymer material was used, the temperature at which the
hole cap sealing 11 was formed was set to be lower than the tctnperature at which the barriers 10
was formed.
30 [0078]
As the method of forming the hole cap sealing 11, a printing mask having an
opening at a desired position was used to apply paste to be used for the hole cap sealing 11 at a
desired position of the channel 12 formed by the barriers 10 using a screen printing method to
form the hole cap sealing 11.
2 1
[0079]
Furthermore. as the method of forming the hole cap sealing I I, using a dispcnser
having a plurality of nozzles arranged at a predetermined position, it was possible to apply paste
to be uscd for the hole cap sealing 11 at a desi~edp osition of tlie channel 12 formed by the
5 barriers 10 using a paste discharging method to form the hole cap sealing I I . For example, for
high polymer application, an ultra-fine needle with a micron-order needle point for medical use
was used. First, the needle was inserted up to the vicinity of the sealing part and the needle was
pulled out while spraying the high polymer.
[0080]
10 Thus, in the present embodiment as in the case of Embodiment 1, it was possible
to prepare a structure of the ceramic honcycomb structure 2 having an outside diamcter
(diamctcr) of 5.66 inches, a total length of 6 inches, with the barriers 10 having a thickness of
0.32 mm, a pitch of 1.57 mm, and an initial pressure loss of 0.85 mmAq (at 7.5 Nm31min).
Embodiment 5
15 [0081]
An absorbent was prepared using the following method for the ceramic
honeycomb structure 2 prepared in Etnbodiment 2 or the like.
[0082]
As tlie high polymer material 13 used for the adsorptive material, a material
20 including at least one type of high polymer containing two or more chemically equivalent amino
groups with respect to a repeating unit was modified. It has been confirmed ttirough an
experiment that the high polymer material 13 has a feature of adsorbing organic matter that
contaminates the reverse osmosis membrane 3 used in the post-process of tlie adsorption module
1.
25 [0083]
As an example ofthe adsorptive material 13, polyamide was dissolved in Nmethyl
pyrrolidone (NMP) to prepare a 0.5% polyamide NMP solution. The polyamide
obtained by polyn~erizing4 , 4'-oxydianiline and isoplitlialoyl dict~loridea s monomers was used.
[0084]
30 To prevent contamination ofthe reverse osmosis membrane 3 used in the postprocess
of the adsorption module 1, the high polymer material 13 was modified on the surface of
the barriers 10 of the porous ceramic honeycomb structure 2 used for the adsorption module 1 or
the top layer of the surface of the fine communication holes in the barriers 10. The high
polymer material 13 was applied to any one of combinations of all or sotlie of the barriers I0 of
thc porous ceramic honeycomb structure 2. the first-half and the last-half thereof, only the inner
walls of tlie barriers I0 of the first-half part, and only the inner walls of the of the barriers I0 of
the last-half part.
5 roo851
The method of applying the high poly~nerm aterial 13 to tlie porous ceramic
honeycomb structure 2 is similar to some methods used for when forming the hole cap sealing
1 I, and using a dispenser having a plurality of nozzles arranged at a desired position, the high
poly~nerm aterial 13 was formed by spraying and applying tlie high poly~nerm aterial 13 at a
10 desired position in the channel 12 formed by the barriers 10 ofthe porous ceramic honeycomb
structure 2 using a discharging method.
[0086]
For example, an ultra-fine needle with a micron-order needle point for medical
use was used for high polyrner application. It is possible to use a method of inserting tlie needle
15 up to the vicinity of the end of the hole cap sealing 11 first and pulling out the needle while
spraying the high polymer. The high polymer material 13 that adsorbs and removes organic
Inalter was applied to all or some of the surfaces of the barriers 10 and the surfaces of inside
holes of0.005 to 0.050 rnln to a degree of thicktiess that will not till the inner fine holes of the
barriers 10, preferably 100 nni or less. After applying the high polymer material I3
20 (polyamide) used for the adsorptive niaterial into the desired channel 12 ofthe ccramic
honeycomb structure 2, the ceramic honeycotnb structure 2 was dried by an oven at 130°C for 24
hours.
[00871
In this case, water passed through tlie barriers 10 with substantially no rcsistance
25 and the applied high polymer nlaterial 13 could adsorb and remove water-dissolved organic
matter.
1100881
'I'he ~nechanisnin which the high polytner material 13 adsorbs water-dissolved
organic mattcr is affccted by intermolecular interaction. It is preferable to use polymer
30 containing an -NH- bond having high affinity with a carbonyl group, carboxyl group or aromatic
ring as the high polymer material 13 for adsorption based on an analysis of adsorbed organic
matter. Exarnples of inclusion of an -NH- bond in the repeating unit of poly~nerin clude
polyamide, polyimide, polyurethane, urea resin, polypeptide (protein), polyethyleneimine,
poiybenzimidazole, and polybenzoxazole. Materials containing an -NH- bond in a side chain or
principal chain may also be used as other materials. Fig. 6 shows a chemical structure of the
high polymer. Exa~nplesth ereof include polyallylamine and polyvinylamine. Ftirtlierniore,
materials containing a carbonyl group and siloxane structure in the principal chain or side chain
rnay also be used for afinity with an -NH- bond or siloxanc and the like. Furthern~oret,l ie
5 structure included in the principal chain or side chain is not limited to one type, and inclusion of
a plurality of structures makes it possible to adsorb a wide range of types of ~nixturesc ontained
in water and improve the adsorption efficiency.
[0089]
Polyamide and cellulose acetate in general use may be used as the adsorption high
10 polymer material 13, but the adsorption high poly~nerm aterial 13 is not limited to these.
[0090]
Furthermore, a photocatalyst may be supported for the porous ceramic
honeycomb structure 2 or high poly~nerm aterial 13 to decompose organic matter. As the
photocatalyst, titanium oxide, strontium titanate, zinc oxide, iron oxide, tungsten oxide or the
15 like !nay be used but the photocatalyst is not limited to these.
[0091]
By performing purification treatment on water before treatment using the porous
ceramic honeyco~nbs tructure 2 with the modilied adsorption high poly~nerm aterial 13, it is
possible to efficiently remove organic matter with a large surface area, and sincc thc channel 12
20 of the adsorption nodule 1 is wide, clogging is less likely to occur and it is possible to reduce the
frequency of cleaning the reverse osmosis ~ne~nbran3 ein the post-process of the adsorption
module I and reduce the running cost.
LO0921
I3y perfomling the pre-treatment process of the reverse os~nosism cmbrane 3
25 using such an adsorptive material 13, it is possible to selectively adsorb only organic matter
which is the cause ofperfor~nanced eterioration of the reverse osmosis tnen~brane3 beforehand
and renlove tlie organic liiatter fro111 within tlie water, and since the amount of organic matter
accu~nulatedin the adsorptive material I3 is small, the adsorptive material 13 is replaced less
frequently, and a low cost pre-treatment method could be obtained by limiting the adsorption
30 function to the outer~nosst urface.
Embodiment 6
[0093]
In the present embodiment, a proof experiment of performance of the adsorption
structure was conducted. The primary treated sewage water supplied to the adsorption module
1 is subjected to a series of treatment such as treatment of removing dust or the like by screening,
treatment whereby a fine suspended material such as sand is settled and removed by adding a
coagulant thereto, and treatment of decomposing organic matter using microorganisms. The
5 primary treated sewage water contains salt and dissolved organic matter. The primary treated
sewage water treated in this way contains dissolved organic matter equivalent to 248 mgil, of
TOC (total organic carbon).
[0094]
The proof experiment was conducted as follows. Using an experiment apparatus
10 simulating the water treatment apparatus in Fig. 1, water before treatment was treated using an
adsorption module in which polyamide is applied to the surface of a ceramic honeycomb as the
high polymer material 13, the water was then treated using a reverse osmosis membrane module
and the amount of organic matter adsorbed to the reverse osmosis membrane 3 was measured
using a size exclusion chromatography (GI'C). Furthermore, for comparison, the adsorption
15 module 1 without application of the high polymer material 13 was prepared and subjected to the
same treatment, and the amount of organic matter adsorbed to the reverse osmosis membrane 3
was compared and examined using the GPC. The GPC condition is as follows. The colu~nn
was one ~nanul:actured by Hitachi Chemical Co., I..td., with model: GL-W550, column
temperature: 4IoC, sample volume 20 PI,, elutit~gs oll~lionp: ure water, flow rate: I .O inL/min,
20 detector (detection wavelength): IJV (220 nm). As a result, the dissolved organic matter was
reduced by an amount equivalent to 12 mdl, of TOC (total organic carbon) after the treatment
using the adsorption module I compared to before the treatment using the adsorption module 1.
LO0951
Furthennore, it was also co~itirmedth at niodified polyamide could remove
25 organic matter in a low molecule region compared to unmodified polyamide. That is, it is
assumed that modified polyamide and unmodif ed polyamide adsorb different types of dissolved
organic matter.
to0961
Furthermore, it could be co~ifirmedt hat with the adsorption module 1 of
30 unmodified polyarnide (material 13 adsorbed to the ceramic honeycomb structure 2 is
unmodified), the dissolved organic matter was equivalent to 226 mg/L ofTOC (total organic
carbon) and dissolved organic matter in the primary treated sewage water could be adsorbed by
alumina groups in the component material formed on the surface ofthe barriers 10 of the
ceramic honeysomb structure 2, confirming that the adsorption module 1 was effective as the
adsorption niodule.
~00971
As described above, it has been confirmed that it is not necessary to modify the
adsorptivc material 13 onto all of the surfaces of the barriers I0 and the surfaces of fine through
5 holes inside the barriers 10 ofthe ceramic honeyc,omb structure 2 used for the adsorption module
1 and dissolved organic matter having a wide range of molecular weights can be adsorbed with
the presence of a partially unmodified portion.
Description of reference numerals
[0098]
1 ... adsorption module
2 ... ceramic honeyco~nbs tructure
3 ... reverse osmosis membrane
4 ... ~nodulc
5 ... water storage tank
6 ... pump
7 ... housing
8 ... support body
9 ... outer wall
I0 ... barrier
I I ... hole cap sealing
12 ... channcl
13 ... high polymer material (adsorptive material)

Claims
[claim 1 ]
An adsorption structure for adsorbing organic matter in a water to be treated,
comprising:
an outer wall?
a plurality of flow paths arranged at an inside of the outer wall, and
a partition wall separating the flow paths from each other,
characterized in that the partition wall includes communication holes which have
diameters less than diameters of the flow paths, and forlii co~nmunicationsb etween the flow
paths to adsorb tlie organic matter.
[claim 21
')'lie adsorption structure according to claim I , characterized in that
the adsorption structure has first and second surfaces opposite to each other,
the flow paths are juxtaposed in a direction perpendicular to longitudinal
directions thereof, and have first flow paths opening onto the first surface and second flow paths
opening onto the second surface.
[claim 31
'The adsorption structure according to claim 2, characterized in that
tlie first flow paths do not open o~itoth e second surhce, and tlie sccond flow
paths do 1101 open onto the first surface.
[clai~n41
'l'hc adsorption structure according to claim 2 or 3, characterized in that
the first flow paths and the second flow paths are arranged alternately in the
direction perpcndicolar to the longitudinal directions.
[claim 51
'The adsorption structure according to ally one of claims 1-4, characterized in that
the partition wall is made of ceramics.
[claim 61
The adsorption structure according to claim 5, characterized in that
the outer wall and the partition wall are made of ceramics honeycomb.
[claim 71
The adsorption structure according to claim 5 or 6, characterized in that
a polymeric material for adsorbing the organic matter is formed on the ceramics.
[claim 81
'Ihe adsorption structure according to any one of claims 2-7, characterized in that
the first flow paths are formed by sealing holes communicating between the first
surface and the second surface at a side ofthe sccond surface with hole cap sealings, and
the second flow paths arc fornlcd by scaling the holes communicating between
the first surface and the second surface at a side of the first surfac,e with the hole cap sealings.
[claim 91
The adsorption structure according to claim 8, characterized in that
a void content of the communication holes is greater than that ofthe hole cap
sealings.
[claim 101
The adsorption structure according to claim 5, characterized in that
a material by which the partition wall is made, includes alumina or a composite
oxide including the alumina.
[claim I I]
The adsorption structure according to claim 10, characterized in that
the alumina or tlie composite oxide included by the material by which the
partition wall is made, is at least one of alu~ninosilicate, sillimanite, mullite, spinel, cordierite,
aluminum titanate, and lithium alurninutn silicate.
[claim 121
The adsorption structure according to claim 10, charactcrizcd in that
a coating including the alumina is formed on at least a part or a whole area ofa
surfacc of the partition wall or surfaces of the communication holes in the partition wall.
[claim 13:l
The adsorption structure according to claim 7, characterizcd in that
as an uppermost layer of a surface of the partition wall or surfaces ofthe
co~nmunicationh oles, at least a part or whole surface area oflhe polymeric material is modified
to include at least one kind ofpolymer including at least 2 equivalents of amino group per
repeating unit.
[claim 141
The adsorption structure according to claim 8, characterized in that
a material by which the partition wall is made and a material by which the hole
cap sealing is made are different from each other.
[claim 151
The adsorption structure according to claim 14, characterized in that the material
by which the hole cap sealing is made, includes at least one of glass, polyimide, polyamidc,
polyimide amide. polyurethane, acrylic, epoxy, polypropylene, and Teflon.
[claim 161
'The adsorption skucture according to claim 14, characterized in that
the material by which the hole cap sealing is made, is o composite material made
of ceramics grains and a polymeric organic material.
[claim 171
The adsorption structure according to claim 16, characterized in that the ceramics
grains used as the material by which the hole cap sealing is made, is at least onc of alumina,
silica, magnesia, titania, zirconia, zircon, cordierite, spinel, aluminu~nti tanatc, and lithium
alu~iiinu~snil icate.
[claim 181
The ad.;orption structure according to claim 16, characterized in that the
polymeric organic material used as the material by which the hole cap sealing is made, is at least
one of polyimide, polyamidc, polyimide amide, polyurethane, acrylic, epoxy, polypropylene, and
Teflon.
[claim 191
The adsorption structure according to claini 7, characteri7,ed in that
a void content of a material of the partition wall is 45% - 70%. a void content ofa
material ofthe hole cap sealirlgs is lcss than the void content of the material of the partition wall
and 0% - 40%, and a thickness of the hole cap sealing is greater than a thickness ofthe partition
wall.
[claim 201
A adsorption module comprising,
the adsorption structure according to any one of claims 1-19,
a housing,
a support member supporting the adsorption structtlre in the housing,
ail inlet for taking in the water to be treated, and
an outlet for discharging the treated water,
characterized in that the inlet is connected to the first flow paths, and
the outlet is connected to the second flow paths.
[claim 211
A producing method of an adsorption structure for adsorbing organic matter in a
water to be treated, comprising:
29
a step of forming an adsorption structure body having a plurality of through-holes
which coln~nunicate between first and second surfaces opposite to each other and which are
separated fi.om each other by a partition wall, the partition wall having cotnmunication holes
making co~n~nunicationbse twccn the through-holes and an adsorption ~naterialf or adsorbing the
organic matter,
a step of sealing the through-holes with hole cap sealing at a side of the first
surface to form second flow paths opening at a side ofthe second surface, and
a step of sealing the through-holes not sealed at the side of the first surface with
the hole cap sealing at the side of the second surface to form second flow paths opening at the
side of the first surfice.
[claim 221
The producing method of the adsorption structure according to claim 2 1 ,
characterized in that a terllperature for forming the hole cap sealings is lower than
a temperature for forming the partition wall.
[claim 231
The producing method of the adsorption structure according to claim 21,
characterized in that as a method for forming the hole cap sealings, a printing
Inask including openings at desired posiliolis is used, and the hole cap sealings are formed by a
screen printing with a paste used for the hole cap scalings at ilic desired positions ofthe flow
paths fortiled by tlie partition wall.
[claim 241
The producing method ofthe adsorption structure according to clai1il21,
characterized in that as a method for forming the hole cap sealings, a dispenser
including a plurality of nozzles arranged at desircd positions is used, and the hole cap sealings
are formed by a paste emission with a paste used for the hole cap sedli~~gats predetermined
positions in the flow paths formed by the partition wall.
Iclaim 251
'She producing method of the adsorption structure according to claim 21,
characterized in that the method comprises a step of forming a polymer illaterial
adsorbing organic ~noleculeso n the partition wall.