Title of Invention

INDUSTRIAL EVAPORATION APPARATUS

Abstract It is an object of the present invention, in the case of an apparatus in which a liquid containing material having a lower boiling point than that of the liquid is made to flow down along an external surface of a guide, during which time the lower boiling point material is evaporated, to provide a specific apparatus that can be operated stably for a prolonged period of time on an industrial scale such that not less than 1 ton/hr of the liquid is subjected to the evaporation, and furthermore to provide a specific industrial evaporation apparatus in which there are no problems due to degeneration caused by some of the liquid residing in the apparatus for a prolonged period of time. The present inventors have reached to the present invention upon discovering that the above object can be attained, and a high-quality and high-purity concentrated liquid or condensation polymer or thermoplastic polymer can easily be obtained, by using an industrial evaporation apparatus having a specified structure in which there are guides that do not themselves have a heat source, a flow path controlling member having a function of making the liquid fed onto a perforated plate from a liquid receiving port flow mainly from a peripheral portion toward a central portion of the perforated plate is provided in a liquid feeding zone, and formulae (1) to (5), or formulae (1) to (10), or formulae (1) to (12), are satisfied.
Full Text A0501 UP24_KAN
INDUSTRIAL EVAPORATION APPARATUS
Technical Field
The present invention relates to a novel industrial evaporation apparatus.
35 More particularly, the present invention relates to an apparatus in which a liquid
containing a material having a lower boiling point than that of the liquid is made to
flow down along an external surface of a guide that does not themselves have a heat
source, during which time the lower boiling point material is evaporated.
10 Background Art
It is well-known that various industrial evaporation apparatuses are used to
remove volatile components and/or low boiling point components by evaporation
from a liquid and thus concentrating the liquid. For example, Kagaku Kogyo Binran
("Chemical Engineers' Handbook") 6th Edition (edited by the Society of Chemical
15 Engineers, Japan, 1999: Non-Patent Document 1) (see pages 403-405) describes
the following types of industrial evaporation apparatuses: a submerged combustion
type, a natural circulation immersed tube type, a natural circulation horizontal tube
type, a vertical short tube type, a vertical long tube climbing film type, a horizontal
tube falling film type, a vertical long tube falling film type, a forced circulation
20 horizontal tube type, a forced circulation vertical tube type, coil type, an agitated film
type, a centrifugal thin film type, a plate type, and a flash evaporation type. Of
these industrial evaporation apparatuses, for a system in which the liquid is made to
flow from the top downward, there are the horizontal tube falling film type, the vertical
long tube falling film type, the forced circulation horizontal tube type, the forced
25 circulation vertical tube type, and the agitated film type. With the exception of the
agitated film type, all of these are of the same form as a multi-tube cylindrical heat
l

A0501 UP24_KAN
exchanger. For the agitated film type, scrapers are rotated over a cylindrical or
conical inner surface which is heated through an outer heat source, thus scraping a
liquid film off from the heat transfer surface as the liquid film is formed thereon,
whereby the liquid is concentrated through evaporation while making the evaporation
5 uniform and promoting heat transfer. Moreover, with the horizontal tube falling film
type or the forced circulation horizontal tube type, which are of the heat exchanger
type, the liquid is concentrated through evaporation while being made to flow in the
form of a liquid film over external surfaces of horizontally installed tubes; the tubes
themselves are heated through a heating medium such as steam flowing
10 therethrough.
In terms of the flow of the liquid, the industrial evaporation apparatuses
closest to the type of the present invention are the vertical long tube falling film type
and the forced circulation vertical tube type, but these are of a type in which the
liquid is concentrated through evaporation while descending in the form of a film
15 through vertically installed tubes, as opposed to the system of the present invention
in which the liquid is made to flow down along external surfaces of guides, and
moreover the tubes through which the liquid flows down are themselves heated by a
heating medium that flows over the outside (trunk portion) of each of the tubes,
unlike in the present invention in which the guides do not themselves have a heat
20 source.
Moreover, strand evaporators in which a melt of a polymer or the like is
extruded in the form of strands or filaments from a perforated plate into an
evaporation zone, and the polymer melt is concentrated through evaporation while
falling down freely are also known (See Patent Document 1: U.S. Patent No.
25 3110547; Patent Document 2: Japanese Patent Publication No. 30-2164). However,
there are drawbacks with such a strand evaporator, for example, because the liquid
2

A0501 UP24_KAN
to be concentrated is allowed to fall down freely, the residence time in the
evaporation zone is short, and hence the evaporating efficiency is poor, and
moreover the strands or filaments sway sideways in the evaporation zone and are
thus liable to fuse to one another, and hence continuous stable operation is difficult.
5 Apparatuses in which a polyamide, a polyester or the like is produced while making a
monomer mixture or prepolymer flow down along linear supports have also been
proposed (See, for example, Patent Document 3: U.S. Patent No. 3044993; Patent
Document 4: Japanese Patent Publication No. 48-8355, Patent Document 5:
Japanese Patent Application Laid-open No. 53-17569; Patent Document 6:
10 Japanese Patent Application Laid-open No. 60-44527; Patent Document 7:
Japanese Patent Application Laid-open No. 61-207429). Furthermore, an
apparatus in which wire loops are installed in an evaporation zone, and a
high-viscosity polymer melt is concentrated through evaporation or has gas removed
therefrom while being made to flow down along the wire loops has been proposed,
15 and it has been stated that such an apparatus can be advantageously used for
subjecting a polycarbonate solution or melt in particular to concentration through
evaporation or gas removal (See Patent Document 8: International Publication WO
20 02/051606); this method is substantially the same as a method and apparatus
already proposed by the present inventors in which a polycarbonate is produced by
20 polymerizing a molten polymerization starting material while making the molten
polymerization starting material flow down along wires or perforated sheet-shaped
guides (See Patent Document 9: International Publication WO 99/36457). However,
with such an apparatus having the wires or the perforated sheet-shaped guides,
there have been no specific disclosures or suggestions relating to the scale or use of
25 an apparatus which can carry out the evaporation operation stably for a prolonged
period of time on an industrial scale such that not less than 1 ton / hr of the liquid is
3

A0501 UP24_KAN
subjected to the evaporation.
Furthermore, with evaporation apparatuses known so far, there has been no
description of means for avoiding degeneration such as discoloration, gelation,
crosslinking, production of an ultra-high molecular weight, solidification, scorching or
5 carbonization due to some of the liquid residing in the apparatus for a prolonged
period of time. In particular, in the case of an apparatus for evaporating lower
boiling point material from a liquid having a relatively high viscosity, it has been
revealed for the first time through carrying out prolonged continuous operation that
such degeneration occurs, then the degenerated material progressively or suddenly
10 becomes mixed in the concentrated liquid, bringing about problems of discoloration
and contamination with solid foreign material, which are fatal for the concentrated
product such as polymer etc.
However, it is clear that with the evaporation apparatuses known so far, no
consideration whatsoever has been given to such degeneration upon prolonged
15 operation. For example, according to FIG. 1 in Patent Document 5, which relates to
an evaporation apparatus that uses linear supports, it is clear that there is much
so-called "dead space" where the polymer resides for a prolonged period of time and
is thus heated between a hole portion of a perforated plate and an internal sidewall
surface of a hollow body, and no means whatsoever has been adopted for reducing
20 this "dead space". Accordingly, the high-viscosity material fed in from a
high-viscosity material feeding port (7) resides for a prolonged period of time in the
"dead space" between the perforated plate (3) and the internal sidewall surface of
the hollow body, and hence the above problems occur inevitably. Moreover, even in
recently proposed by Patent Document 8, no means whatsoever has been adopted
25 for reducing "dead space" in a distributor pipe 3 (FIG. 2), or a feeding zone from
which feeding is carried out onto a perforated plate (FIG. 3a).
4

A0501 UP24_KAN
Disclosure of Invention
It is an object of the present invention, in the case of an apparatus in which a
liquid containing material having a lower boiling point than that of the liquid is made
5 to flow down along an external surface of a guide that does not themselves have a
heat source, during which time the lower boiling point material is evaporated, to
provide a specific apparatus that can be operated stably for a prolonged period of
time on an industrial scale such that not less than 1 ton / hr of the liquid is subjected
to the evaporation, and furthermore to provide a specific industrial evaporation
10 apparatus in which there are no problems due to degeneration caused by some of
the liquid residing in the apparatus for a prolonged period of time.
The present inventors carried out studies into using in various applications a
previously proposed guide-contacting downflow type polymerization apparatus in
which a molten prepolymer is subjected to polymerization while being made to fall
15 down along guides such as wires. As a result, the present inventors discovered an
industrial evaporation apparatus having a specified structure characterized as
described below in which the above object can be attained, thus reaching to the
present invention. That is, the present invention provides:
1. An industrial evaporation apparatus in which a liquid containing a material having
20 a lower boiling point than that of said liquid is made to flow down along an external
surface of a guide that does not themselves have a heat source, during which time
said lower boiling point material is evaporated, said evaporation apparatus
comprises:
(1) said evaporation apparatus comprising a liquid receiving port; a liquid
25 feeding zone for feeding said liquid via a perforated plate to said guide provided in
an evaporation zone; said evaporation zone having a plurality of guides that extend
5

A0501 UP24_KAN
downward within a space enclosed by said perforated plate, a side-wall casing, and
a bottom-wall casing; an evaporated material outlet provided in said evaporation
zone; and a liquid discharge port provided in a lowermost portion of the bottom-wall
casing;
5 (2) a flow path controlling member which has a function of making said liquid
fed onto the perforated plate from said liquid receiving port flow mainly from a
peripheral portion toward a middle portion of the perforated plate being provided in
said liquid feeding zone;
(3) an internal sectional area A (m2) taken through a horizontal plane of the
10 side-wall casing of said evaporation zone satisfying the following formula (1):
0.7≤ A≤ 300 (1);
(4) a ratio between said A (m2) and an internal sectional area B (m2) taken
through a horizontal plane of the liquid discharge port satisfying the following formula
(2):
15 20 ≤ A/B ≤ 1000 (2);
(5) the bottom-wall casing constituting the bottom portion of said evaporation
zone being connected at an internal angle C (°) to said side-wall casing on said
bottom-wall casing, wherein said angle C (°) satisfies the following formula (3):
110 ≤ C≤ 165 (3);
20 (6) a length h (cm) of each of said guides satisfying the following formula (4):
150 ≤ h≤5000 (4);
(7) a total external surface area S (m2) of said guides satisfying the following
formula (5):
2≤ S≤ 50000 (5),
25 2. The industrial evaporation apparatus according to item 1, wherein not less than 1
ton / hr of said liquid is subjected to the evaporation,
6

A0501 UP24_KAN
3. The industrial evaporation apparatus according to item 1 or 2, wherein an angle
E (°) between an internal sidewall surface of said liquid feeding zone and said
perforated plate satisfies the following formula (6):
100≤ E 5 4. The industrial evaporation apparatus according to any one of items 1 to 3,
wherein said side-wall casing of said evaporation zone is cylindrical with an inside
diameter D (cm) and a length L (cm), the bottom-wall casing connected at a bottom
portion of said side-wall casing is conical, and the liquid discharge port, which is in
the lowermost portion of the conical bottom-wall casing, is cylindrical with an inside
10 diameter d (cm), wherein D, L and d satisfy the following formulae (7), (8), (9) and
(10):
100 ≤ D≤ 1800 (7)
5 ≤ D/d ≤ 50 (8)
0.5 ≤ L/D≤ 30 (9)
15 h-20 ≤ L ≤h + 300 (10),
5. The industrial evaporation apparatus according to any one of items 1 to 4,
wherein the h satisfies the following formula (11):
400 6. The industrial evaporation apparatus according to any one of items 1 to 5,
20 wherein one of said guides is cylindrical, or pipe-shaped and made to be such that
the liquid and/or gaseous material cannot enter therein, with an outside diameter r
(cm), wherein r satisfies the following formula (12):
0.1 ≤ r ≤ 1 (12),
7 The industrial evaporation apparatus according to any one of items 1 to 5,
25 wherein said guides comprise guides according to claim 6, and the guides are joined
together by transverse supports,
7

A0501 UP24_KAN
8. The industrial evaporation apparatus according to any one of items 1 to 5,
wherein said guides comprise guides according to claim 6, and form one of a
grid-like or mesh-like guide structure in which the guides are fixed together by
transverse supports, a three-dimensional guide structure in which a plurality of
5 grid-like or mesh-like guide structures are arranged in front of and behind one
another and are fixed together by transverse supports, and a jungle-gym-like
three-dimensional guide structure in which the guides are fixed together in front of
and behind, and left and right of, one another by transverse supports,
9. The industrial evaporation apparatus according to any one of items 1 to 8,
10 wherein said liquid is a melt of a monomer or a mixture of two or more kinds of
monomers for producing a condensation polymer, and/or a prepolymer of the
condensation polymer, and/or the condensation polymer, the lower boiling point
material is a by-produced material and/or oligomer produced through condensation
polymerization, and said industrial evaporation apparatus is a condensation polymer
15 polymerization apparatus for removing said lower boiling point material from said
melt by evaporation so as to increase a polymerization degree of the prepolymer of
the condensation polymer and/or the condensation polymer,
10. The industrial evaporation apparatus according to item 9, wherein the
condensation polymer is a polyester, a polyamide, or a polycarbonate,
20 11. The industrial evaporation apparatus according to any one of items 1 to 8,
wherein said liquid is a melt of a thermoplastic polymer A, said lower boiling point
material is a monomer, an oligomer, and a by-produced material contained in the
polymer, and the industrial evaporation apparatus is a purifying apparatus for
removing said lower boiling point material from said melt by evaporation so as to
25 increase purity of said thermoplastic polymer A,
12. The industrial evaporation apparatus according to item 11, wherein said
8

A0501 UP24_KAN
thermoplastic polymer A is a polystyrene-based polymer, a polyvinyl chloride-based
polymer, a polyvinylidene chloride-based polymer, a polyacrylonitrile-based polymer,
a polyacrylic ester-based polymer, a polymethacrylic ester-based polymer, or a
thermoplastic elastomer,
5 13. The industrial evaporation apparatus according to any one of items 1 to 8,
wherein said liquid is a solution of a thermoplastic polymer B, said lower boiling point
material is a solvent in which said thermoplastic polymer is dissolved and/or a
monomer, an oligomer, and a by-produced material contained in said polymer
solution, and said industrial evaporation apparatus is a separation recovery /
10 purification apparatus for removing said low boiling point material from said solution
by evaporation so as to separate and thus recover said thermoplastic polymer from
said solution and increase purity of said thermoplastic polymer.
Advantageous Effects of the Invention
15 The industrial evaporation apparatus according to the present invention is an
evaporation / concentration apparatus in which a large amount of a liquid can be
efficiently concentrated through evaporation stably for a prolonged period of time,
and in which not less than 1 ton / hr of the concentrated liquid can be produced,
without occurring degeneration of the liquid over a prolonged period of time. In
20 particular, the industrial evaporation apparatus according to the present invention
achieves excellent effects in the concentration through evaporation of a liquid having
a relatively high viscosity. With the apparatuses known so far for concentrating
such liquids having the relatively high viscosity through evaporation, there have been
places where some of the liquid resides while being heated for a prolonged period of
25 time, whereupon this liquid undergoes degeneration such as discoloration, gelation,
crosslinking, production of an ultra-high molecular weight, solidification, scorching,
9

A0501 UP24_KAN
carbonization or the like, and it has been found that the degenerated material mixes
in the concentrated liquid progressively or suddenly, causing a deterioration in color
and properties of the concentrated liquid. The industrial evaporation apparatus
according to the present invention is a continuous evaporation apparatus that does
5 not suffer from such drawbacks, and in particular achieves excellent effects as a
polymerization apparatus for a condensation polymer, a purifying apparatus for a
thermoplastic polymer, or an apparatus for separating and thus recovering the
polymer from a thermoplastic polymer solution and purifying the polymer. That is,
the industrial evaporation apparatus according to the present invention is an
10 apparatus that enables a high-performance and high-purity polymer to be produced
with high productivity of not less than 1 ton / hr stably for a prolonged period of time
with no discoloration or contamination with foreign material caused by production of
thermally degenerated material. Furthermore, in the case that the evaporation
apparatus according to the present invention is used as a polymerization apparatus,
15 it can be made to be such that there is very little variation in molecular weight.
Brief Description of Drawings
FIG 1 is a schematic sectional view showing an industrial evaporation
apparatus according to the present invention;
20 FIG 2 is a schematic sectional view showing a cylindrical industrial
evaporation apparatus according to the present invention;
FIG. 3 is a sectional view showing schematically an upper portion of the
industrial evaporation apparatus according to the present invention;
FIG 4 is a sectional view showing schematically an upper portion of the
25 industrial evaporation apparatus of the present invention;
FIG 5 is a sectional view showing schematically means for eliminating "dead
10

A0501 UP24_KAN
space" between an internal wall of a liquid feeding zone, and a perforated plate and
a flow path controlling member; and
FIG 6 is a sectional view showing schematically means for eliminating "dead
space" between an internal wall of the liquid feeding zone, and a perforated plate
5 and the flow path controlling member.
1: liquid receiving port, 2: perforated plate, 3: liquid feeding zone, 4: guide, 5:
evaporation zone, 6: evaporated material outlet, 7: liquid discharge port, 8: liquid
discharge pump, 9: an inert gas feeding port according to need, 10: side-wall casing
of evaporation zone, 11: bottom-wall casing of evaporation zone, 20: liquid outlet, 13:
10 flow path controlling member, 21: example of hole of perforated plate, 22: inner
sidewall surface of liquid feeding zone, 23: upper inner wall surface.
Best Mode for Carrying Out the Invention
The present invention is based on the discovery that to attain the above
15 object for a continuous type evaporation apparatus, various conditions must be
satisfied. The present invention will now be described in more detail with reference
to sectional views (FIGS. 1 and 2) illustrating the concept of the evaporation
apparatus according to the present invention and sectional views (FIGS. 3 and 4)
showing a part of the evaporation apparatus.
20 A liquid receiving port 1 is preferably provided in a top of a liquid feeding
zone 3. There may be such a liquid receiving port 1 in one place or in a plurality of
places, the at least one liquid receiving port 1 preferably being disposed such that
the liquid in the liquid feeding zone 3 can be fed onto a perforated plate 2 as
uniformly as possible. In the case that there is a liquid receiving port 1 in only one
25 place, the liquid receiving port 1 is preferably provided in a central portion of the top
of the liquid feeding zone 3. A flow path controlling member 20 having a function of
11

A0501 UP24_KAN
making the liquid fed onto the perforated plate 2 from the liquid receiving port 1 flow
mainly from a peripheral portion toward a central portion of the perforated plate 2
must be provided in the liquid feeding zone 3. The flow path controlling member 20
has an effect of making the liquid flow from the peripheral portion toward the central
5 portion of the perforated plate 2, thus preventing the liquid from residing for a
prolonged period of time in a space between holes (e.g. 21) in the perforated plate 2
and an internal sidewall surface 22 of the liquid feeding zone 3. The liquid made to
flow mainly from the peripheral portion toward the central portion of the perforated
plate 2 is thus fed onto guides 4 from the holes arranged between the peripheral
10 portion and the central portion of the perforated plate 2.
The flow path controlling member 20 may have any shape so long as the
effects of the flow path controlling member 20 can be achieved, but the outline of a
cross section of the flow path controlling member 20 is preferably similar figure to the
outline of a cross section of the perforated plate 2. As used herein, the term" the
15 cross section of the flow path controlling member 20" refers to a section obtained by
cutting through the flow path controlling member 20 in a transverse direction at the
place where this section exhibits the maximum area. A preferable range for the
spacing between the flow path controlling member 20 and the internal sidewall
surface 22 of the liquid feeding zone 3 varies according to the amount and viscosity
20 of the liquid to be processed and so on, but in the case the that the evaporation
apparatus is used as a polymerization apparatus, a polymer purifying apparatus or
the like with the liquid to be subjected to the evaporation having a relatively high
viscosity, a range of from 1 to 50 cm is generally preferable, with from 2 to 30 cm
being more preferable, and from 3 to 20 cm being yet more preferable. The spacing
25 between a top internal wall surface 23 of the liquid feeding zone 3 and the flow path
controlling member 20 may be any spacing, but is preferably made to be such that
12

A0501 UP24_KAN
the residence time of the liquid in the liquid feeding zone 3 is as short as possible.
For this reason, this spacing is generally in a range of from 1 to 200 cm,
preferably from 2 to 170 cm, more preferably from 3 to 150 cm. The flow path
controlling member 20 can be made to be such that the spacing between the top
5 internal wall surface 23 of the liquid feeding zone 3 and the flow path controlling
member 20 is substantially the same from the liquid receiving port 1 to the internal
side wall surface 22 of the liquid feeding zone 3, but can also be made to be such
that this spacing gradually narrows, or conversely gradually widens. Moreover, the
spacing between the flow path controlling member 20 and the perforated plate 2 is
10 generally from 1 to 50 cm, preferably from 2 to 30 cm, more preferably from 3 to 20
cm. The flow path controlling member 20 can be made to be such that the spacing
between the perforated plate 2 and the flow path controlling member 20 is
substantially the same from the internal side wall surface 22 of the liquid feeding
zone 3 to the central portion of the perforated plate 2, or can also be made to be
15 such that this spacing gradually narrows, or conversely gradually widens, but is
preferably made to be such that the spacing is substantially the same, or gradually
narrows.
The flow path controlling member 20 obstructs the liquid fed in from the liquid
receiving port 1 from being led directly to the holes in the perforated plate 2, and
20 hence may also be thought of as being a kind of baffle. Note that in the case that
the perforated plate 2 has a large area, it is also preferable for some of the liquid fed
in to be made to take a short cut to the vicinity of the central portion of the perforated
plate 2 without passing the peripheral portion of the perforated plate 2, in which case
it is preferable to provide a hole in one place or a plurality of places in the vicinity of a
25 central portion of the flow path controlling member 20 or another suitable portion for
this purpose. So that "dead space" is not created in the liquid feeding zone 3, it is
13

A0501 UP24_KAN
also preferable for the angle E (°) between the internal sidewall surface 22 of the
liquid feeding zone 3 and the perforated plate 2 to satisfy the following formula (6):
100 ≤ E Here, in the case that the internal sidewall surface 22 is planar, E is an angle
5 between the internal sidewall surface 22 and the perforated plate 2 in a section taken
through a plane perpendicular to both the plane of the internal sidewall surface 22
and an upper surface of the perforated plate 2. Alternatively, in the case that the
internal sidewall surface 22 is a concave curved surface, E is an angle between the
upper surface of the perforated plate 2 and a tangent to the internal sidewall surface
10 22 at the point where the internal sidewall surface 22 starts to rise up in a section
taken through a plane perpendicular to both the concave surface of the internal
sidewall surface 22 and the upper surface of the perforated plate 2. Moreover, it is
also preferable to devise the evaporation apparatus such that the vicinity of the joint
between the top internal wall surface 23 and the internal sidewall surface 22 of the
15 liquid feeding zone 3 does not become "dead space". It is preferable to make an
angle between the top internal wall surface 23 and the internal sidewall surface 22
be greater than 90°, or 90° or close thereto, since in this case the vicinity of the joint
is concave and hence liquid does not stagnate here.
The internal sectional area A (m2) taken through a horizontal plane (plane
20 a-a1) of a side-wall casing 10 of an evaporation zone 5 must satisfy the following
formula (1):
0.7≤ A≤ 300 (1).
Furthermore, a ratio between A (m2) and the internal sectional area B (m2)
taken through a horizontal plane (plane b-b') of a liquid discharge port 7 must satisfy
25 the following formula (2):
20≤ A/B≤ 1000 (2).
14

A0501 UP24_KAN
A/ B must satisfy the above formula (2) so that the liquid and polymer that
have been concentrated through evaporation, or the melt whose viscosity has been
increased without bringing about a reduction in the quality of the concentrated liquid
can be discharged.
5 Furthermore, a bottom-wall casing 11 constituting a bottom portion of the
evaporation zone 5 is connected at an internal angle C (°) to the side-wall casing 10
thereabove, and the angle C (°) must satisfy the following formula (3):
110≤ C ≤165 (3).
To keep down the equipment cost, C is preferably as close as possible to 90°,
10 but to move the concentrated liquid falling down from the lower ends of the guides 4,
and the melt whose viscosity has been increased without bringing about a reduction
in the quality of the concentrated liquid, to the liquid discharge port 7, C must satisfy
the above formula (3).
Furthermore, the length h (cm) of each of the guides 4 must satisfy the
15 following formula (4):
150≤h≤ 5000 (4).
It is undesirable for h to be shorter than 150 cm, since then the concentration
or polymerization cannot be carried out sufficiently. It is undesirable for h to be
longer than 5000 cm, since then the difference in the viscosity of the liquid between
20 the top and the bottom of each guide 4 becomes too great, thereby resulting in
tending to be much variation in the concentration degree or polymerization degree.
Furthermore, the total external surface area S (m2) of the guides 4 must
satisfy the following formula (5):
2≤ S≤ 50000 (5).
25 If S is less than 2 m2, then the desired amount of the liquid subjected to the
evaporation of not less than 1 ton / hr or the desired production amount of the
15

A0501 UP24_KAN
polymer produced cannot be attained. Moreover, to attain such a production
amount while keeping down the equipment cost, and to eliminate variation in
properties, S must be made to be not more than 50000 m2.
It has been discovered that the evaporation apparatus according to the
5 present invention satisfying the above various conditions not only solves the
problems of the evaporation apparatuses known so far, but moreover, surprisingly,
achieves excellent effects as described earlier, it being possible to produce a
high-quality and high-performance concentrated liquid or polymer with no
discoloration in an amount of not less than 1 ton / hr stably for a prolonged period of
10 time of not less than several thousand hours, for example hot less than 5,000 hours.
It is supposed that the reason why the industrial evaporation apparatus
according to the present invention exhibits such excellent effects is that, in addition
to the various reasons described above, a combined effect arises when the above
conditions are combined. For example, it is supposed that this is because guides 4
15 having a high surface area satisfying the formulae (4) and (5) are very effective for
efficient internal stirring and surface renewal of a large amount of liquid or
prepolymer or polymer fed in at a relatively low temperature, and hence evaporation
of the lower boiling point material can be carried out efficiently, which is useful for
obtaining a large amount of not less than 1 ton / hr of high-quality concentrated liquid
20 or polymer, and moreover the angle C satisfying the formula (3) makes it possible to
shorten the time taken for the large amount of the high-quality concentrated liquid or
polymer falling down from the guides 4 to be discharged from the discharge port 7,
and thus reduce the heat history.
Note that the performance of the evaporation apparatus on an industrial
25 scale can only be established through prolonged operation using large-scale
production equipment, and it goes without saying that the cost of the production
16

A0501 UP24_KAN
equipment here is an important factor that must be taken into consideration.
Another advantageous effect of the present invention is that the equipment
cost-to-performance ratio for the evaporation apparatus according to the present
invention can be made lower than with the conventional evaporation apparatuses or
5 polymerization apparatuses.
Specified conditions and required ranges for dimensions, angles and so on
for the industrial evaporation apparatus according to the present invention have been
described above, but more preferable ranges are as follows: A more preferable
range for the internal sectional area A (m2) taken through a horizontal plane of the
10 side-wall casing 10 of the evaporation zone 5 is 0.8≤A≤ 250, with 1 ≤ A ≤
200 being yet more preferable.
Moreover, a more preferable range for the ratio between A (m2) and the
internal sectional area B (m2) taken through a horizontal plane of the liquid discharge
port 7 is 25 ≤A/B ≤900, with 30 ≤ A/B≤ 800 being yet more preferable.
15 Moreover, a more preferable range for the internal angle C (°) of the bottom-wall
casing 11 constituting the bottom portion of the evaporation zone 5 to the side-wall
casing 10 thereabove is 120 ≤ C≤ 165, with 135 ≤ C≤ 165 being yet more
preferable. Note that in the case of progressively increasing the concentration
degree or polymerization degree using a plurality of evaporation apparatuses, taking
20 the angles for the evaporation apparatuses to be C1, C2, C3 ... respectively, it is
preferable to make C1 ≤ C2 ≤ C3≤ ....
Moreover, the required length h (cm) of each of the guides 4 varies with
factors such as the amount, viscosity and temperature of the liquid to be processed,
the amount and boiling point of lower boiling point material, the pressure and
25 temperature in the evaporation zone, and the required concentration degree or
polymerization degree, but a more preferable range is 200 ≤ h ≤3000, with 400 17

A0501 UP24_KAN
h ≤ 2500 being yet more preferable. Moreover, the required total external surface
area S (m2) of the guides 4 also varies with factors such as the above, but a more
preferable range is 10 ≤S ≤ 40000, with 15 ≤ S ≤30000 being yet more
preferable. The term "total external surface area of the guides" used in the present
5 invention means the total surface area of the guides with which the liquid contacts
when flowing down; for example, in the case of a guide such as a pipe, this means
the surface area of the outside of the pipe, the surface area of the inside surface of
the pipe over which the liquid does not flow down not being included.
In the industrial evaporation apparatus according to the present invention,
10 the shape of the inside section taken through a horizontal plane of the side-wall
casing 10 of the evaporation zone 5 may be any shape, for example polygonal,
elliptical or circular. Operation is generally carried out with the evaporation zone 5
under a reduced pressure, and hence any shape is acceptable so long as this
reduced pressure can be withstood, but a circular shape or a shape close thereto is
15 preferable. The side-wall casing 10 of the evaporation zone 5 is thus preferably
cylindrical. In this case, it is preferable for a conical bottom-wall casing to be
provided at the bottom of the cylindrical side-wall casing 10, with a cylindrical liquid
discharge port 7 being provided in the lowermost portion of the bottom-wall cashing.
In the industrial evaporation apparatus according to the present invention, in
20 the case that each of the side-wall and bottom-wall casings of the evaporation zone
5 comprises a cylindrical portion and a conical portion as described above, and the
liquid discharge port 7 for the concentrated liquid or polymer is cylindrical, taking the
cylindrical portion of the side-wall casing to have an inside diameter D (cm) and a
length L (cm), and taking the liquid discharge port 7 to have an inside diameter d
25 (cm), D, L and d preferably satisfy the following formulae (7), (8), (9) and (10):
100 ≤D ≤ 1800 (7)
18

A0501 UP24_KAN
5 ≤ D/d ≤ 50 (8)
0.5 ≤L/D ≤ 30 (9)
h-20≤ L ≤ h + 300 (10).
For the evaporation apparatus according to the present invention, a more
5 preferable range for D (cm) is 150 ≤ D ≤ 1500, with 200≤ D ≤ 1200 being yet
more preferable. Moreover, a more preferable range for D / d is 6 ≤ D/d ≤ 45,
with 7 ≤ D / d≤ 40 being yet more preferable. Moreover, a more preferable
range for L / D is 0.6 ≤ L / D ≤ 25, with 0.7 ≤ L / D ≤ 20 being yet more
preferable. Moreover, a more preferable range for L (cm) is h -10≤ L ≤ h +
10 250, with h ≤ L≤h + 200 being yet more preferable. If D, d and L do not
simultaneously satisfy all of the above relationships, then it becomes difficult to attain
the object of the present invention.
The precise reason why the evaporation apparatus according to present
invention enables production of a high-quality and high-performance concentrated
15 liquid or polymer having excellent mechanical properties with no discoloration stably
(in the case of producing a polymer, with very little variation in molecular weight etc.)
for a prolonged period of time on an industrial scale with a fast evaporation rate or
polymerization rate is not clear, but is thought to be as follows: That is, according to
the evaporation apparatus of the present invention, the starting material liquid is led
20 from the liquid receiving port 1 via the liquid feeding zone 3 and the perforated plate
2 to the guides 4, and is then concentrated, or has the polymerization degree thereof
increased, while flowing down along the guides 4. Effective internal stirring and
surface renewal of the liquid or molten prepolymer occur naturally as the liquid or
molten prepolymer flows down along the guides, and thus removal of lower boiling
25 point material is carried out effectively, whereby the concentration or polymerization
proceeds at a fast rate. The viscosity increases as the concentration or
19

A0501 UP24_KAN
polymerization proceeds, and hence the adhesion force of the liquid or melt to the
guides 4 increases, and thus the amount of the liquid or melt adhered to each guide
increases toward the bottom of the guide. This means that the residence time of
the liquid or molten prepolymer on the guide, i.e. the evaporation time or
5 polymerization reaction time, increases. Moreover, for the liquid or molten
prepolymer, which flows down under its own weight while being supported on the
guide, the surface area per unit weight is very high, and hence surface renewal is
carried out efficiently. Concentration through evaporation, or increase of molecular
weight in the latter half of polymerization, can thus be attained in a high viscosity
10 region easily, whereas this has been impossible with the conventional evaporation
apparatuses or mechanical agitation type polymerization apparatuses. This is one
of the excellent characteristic features of the evaporation apparatus according to the
present invention.
The only reason that the amount of the liquid or melt adhered to the guides
15 increases in the latter half of the polymerization or the evaporation is because of the
increasing of the adhesive holding force, which corresponds to the increasing of
viscosity, and hence approximately the same amount of the liquid or melt having
approximately the same viscosity is supported at the same height on each of the
plurality of guides. On the other hand, the liquid or melt is continuously fed onto the
20 guides from the top thereof, and hence liquid having approximately the same
viscosity, or melt of increased polymerization degree having approximately the same
melt viscosity, continuously falls down into the bottom portion of the casing from the
lower ends of the guides. That is, liquid of approximately the same viscosity, or
polymer of approximately the same polymerization degree, produced while flowing
25 down the guides collects in the bottom portion of the bottom-wall casing 11, and
hence a concentrated liquid with very little variation in evaporation degree, or a
20

A0501 UP24_KAN
polymer with very little variation in molecular weight, is continuously produced. This
is another one of the excellent characteristic features of the evaporation apparatus
according to the present invention. The concentrated liquid or polymer collected in
the bottom portion of the bottom-wall casing is continuously withdrawn through the
5 liquid discharge port 7 by a discharging pump 8, and in the case of a polymer, is
continuously pelletized via an ordinary extruder or the like. In this case, additives
and so on may be added in the extruder.
The perforated plate 2 in the evaporation apparatus according to the present
invention is generally selected from flat plates, corrugated plates, and plates that are
10 thickened in a central portion thereof; the shape of the cross section of the
perforated plate 2 is generally selected from shapes such as circular, oval, triangular,
and polygonal. The shape of the cross section of each of the holes in the
perforated plate is generally selected from shapes such as circular, oval, triangular,
slit-shaped, polygonal, and star-shaped. The sectional area of the holes is
15 generally in a range of from 0.01 to 100 cm2, preferably from 0.05 to 10 cm2,
particularly preferably from 0.1 to 5 cm2. The spacing between holes, specifically
the distance between hole centers, is generally from 1 to 500 mm, preferably from 25
to 100 mm. The holes in the perforated plate may be holes that penetrate through
the perforated plate, or alternatively pipes may be provided in the perforated plate.
20 Moreover, the holes may be tapered.
The guides in the evaporation apparatus according to the present invention
do not themselves have a heat source such as a heating medium or an electrical
heater therein, and each of the guides is a member for which a ratio of the length in
a direction perpendicular to a horizontal section relative to the average length of the
25 outer periphery of such a horizontal section is very high. This ratio is generally in a
range of from 10 to 1,000,000, preferably from 50 to 100,000. The shape of the
21

A0501 UP24_KAN
horizontal section is generally selected from shapes such as circular, oval, triangular,
square, polygonal, and star-shaped. The shape of this section may be constant, or
may vary, in the length direction. Moreover, each of the guides may be hollow. A
significantly characteristic feature of the present invention is that because the guides
5 do not themselves have a heat source, there is absolutely no risk of thermal
degeneration of the liquid on the surface of the guides.
Each of the guides may be a single wire, a single thin rod, a single thin pipe
made to be such that the liquid or the molten prepolymer cannot enter thereinto, or
the like, or a plurality of such guides may be combined using a method such as
10 twisting together. Moreover, the guides may form a mesh-like structure, or a
punching plate-like structure. The surface of each guide may be smooth, or may be
uneven, and may have projections or the like in places. Preferable guides are
cylindrical ones such as wires or thin rods, thin pipes as described above, mesh-like
guide structures, and punching plate-like guide structures.
15 In the guide-contacting downflow type evaporation apparatus according to
the present invention, which enables production of a high-quality concentrated liquid
or polymer on an industrial scale (in terms of production amount, prolonged stable
production, etc.), a particularly preferable guide structure is one of a type in which a
plurality of guides each having the form of a wire or a thin rod or a thin pipe as
20 described above are joined together at suitable vertical intervals using transverse
supports from the top to the bottom of the guides. Examples are mesh-like guide
structures in which a plurality of guides each having the form of a wire or a thin rod or
a thin pipe as described above are fixed together using transverse supports from the
top to the bottom of the guides at suitable vertical intervals, for example intervals of
25 from 1 to 200 cm, a three-dimensional guide structure in which a plurality of such
mesh-like guide structures are arranged in front of and behind one another and
22+

A0501 UP24_KAN
joined together using transverse supports at suitable vertical intervals, for example
intervals of from 1 to 200 cm, or a jungle-gym-like three-dimensional guide structure
in which a plurality of guides each having the form of a wire or a thin rod or a thin
pipe as described above are fixed together in front of and behind, and left and right
5 of, one another using transverse supports at suitable vertical intervals, for example
intervals of from 1 to 200 cm. The transverse supports are not only useful for
keeping the intervals between the guides approximately constant, but are also useful
for increasing the overall strength of flat or curved guides, or guides forming a
three-dimensional structure. The supports may be of the same material as the
10 guides, or a different material.
In the present invention, in the case that each guide is cylindrical, or has the
form of a pipe made to be such that the liquid or molten prepolymer cannot enter
thereinto, with an outside diameter r (cm), r preferably satisfies the formula (12):
0.1 ≤ r ≤ 1 (12).
15 The guides in the present invention promote concentration through
evaporation or polymerization of the liquid or molten prepolymer as the liquid or
molten prepolymer flows down the guides, and also have a function of holding the
liquid or molten prepolymer for a certain period of time. This holding time is related
to the evaporation time or polymerization reaction time. As described above, as the
20 evaporation or polymerization proceeds, the viscosity of the liquid or melt
progressively increases, and hence the holding time and the amount held
progressively increase. For a given melt viscosity, the amount of the liquid or
molten prepolymer held by the guides varies with the external surface area of the
guides, i.e. in the case of cylindrical or pipe-shaped guides, with the outside
25 diameter.
Moreover, the guides provided in the evaporation apparatus according to the
23

A0501 UP24_KAN
present invention must be strong enough to support their own weight plus the weight
of the liquid or molten prepolymer or polymer being held. For this reason, the
thickness of the guides is important, and in the case of cylindrical or pipe-shaped
guides, the formula (12) is preferably satisfied. If r is less than 0.1, then prolonged
5 stable operation becomes difficult in terms of the strength, whereas if r is greater
than 1, then the guides themselves become very heavy, and hence there are
problems such as having to make the perforated plate very thick so as to hold the
guides in the evaporation apparatus. Moreover, there is an increase in parts where
the amount of the liquid or molten prepolymer or polymer held is too high, resulting in
10 problems such as variation in the concentration degree or the molecular weight
increasing. For such reasons, a more preferable range for r is 0.15 ≤ r ≤ 0.8,
with 0.2 ≤r ≤ 0.6 being yet more preferable.
A preferable material for the guides is one selected from metals such as
stainless steel, carbon steel, hastelloy, nickel, titanium, chromium, aluminum, and
15 other alloys, highly heat-resistant polymeric materials, and so on. Stainless steel is
particularly preferable. Moreover, the surfaces of the guides may be subjected to
any of various treatments as necessary such as plating, lining, passivation treatment,
acid washing, or washing with a solvent, phenol or the like.
There are no particular limitations on the positional relationship between the
20 guides and the perforated plate or the positional relationship between the guides and
the holes in the perforated plate so long as the liquid or starting material molten
prepolymer or polymer can contact the guides and flow down the guides. The
guides and the perforated plate may be in contact with one another, or not in contact
with one another. Although there is no such limitation, it is preferable to provide the
25 guides in correspondence with the holes in the perforated plate. The reason for this
is that design may then be carried out such that the liquid or starting material molten
24

A0501 UP24_KAN
prepolymer or polymer falling down from the perforated plate contacts the guides in
suitable positions.
Specific preferable examples of providing the guides in correspondence with
the holes in the perforated plate include: (1) a method in which the upper end of
5 each guide is fixed to the underside of the flow path controlling member or the like,
and the guides are provided such that each guide penetrates through the vicinity of a
central portion of a hole in the perforated plate; (2) a method in which the upper end
of each guide is fixed to a peripheral portion at an upper end of a hole in the
perforated plate, and the guides are provided such that each guide penetrates
10 through a hole in the perforated plate; and (3) a method in which the upper end of
each guide is fixed to the underside of the perforated plate.
Examples of methods for making the liquid or starting material molten
prepolymer or polymer pass through the perforated plate and flow down along the
guides are a method in which the liquid or starting material molten prepolymer or
15 polymer is allowed to flow down through its own weight or the liquid head, and a
method in which the liquid or starting material molten prepolymer or polymer has
pressure applied thereto using a pump or the like and is thus extruded from the
perforated plate. A preferable method is one in which a prescribed amount of the
liquid or starting material molten prepolymer or polymer is fed into the liquid feeding
20 zone of the evaporation apparatus under pressure using a feed pump, and then the
liquid or starting material molten prepolymer or polymer thus led onto the guides via
the perforated plate flows down along the guides under its own weight.
The evaporation apparatus according to the present invention is an
apparatus for evaporating lower boiling point material from a liquid containing this
25 lower boiling point material, i.e. containing material having a lower boiling point than
that of the liquid. The liquid may be any liquid. The liquid may be at room
25

A0501 UP24_KAN
temperature, but is generally fed into the evaporation apparatus from the liquid
receiving port in a heated state. Moreover, it is generally preferable for a jacket or
the like to be provided on an outer wall of the evaporation apparatus. If necessary,
heating is then carried out by passing steam, a heating medium or the like through
5 the jacket, thus heating or maintaining the temperature of the liquid feeding zone, the
flow path controlling member, the perforated plate, or the evaporation zone.
The evaporation apparatus according to the present invention is not only
used as an apparatus for concentrating a liquid, but also is particularly preferably
used as an evaporation apparatus for a liquid having a relatively high viscosity, for
10 example as a polymerization apparatus for a condensation polymer, a purifying
apparatus for a thermoplastic polymer containing low boiling point material such as
monomer, oligomer and by-produced material, or an apparatus for separating and
thus recovering the polymer from a thermoplastic polymer solution.
It is thus preferable to use the industrial evaporation apparatus according to
15 the present invention as a polymerization apparatus for a condensation polymer, in
the case that the liquid is a melt of a monomer or a mixture of a plurality of
monomers for producing a condensation polymer, and/or a prepolymer of the
condensation polymer, and/or the condensation polymer, and the low boiling point
material comprises a by-produced material and/or an oligomer produced through the
20 condensation polymerization, for removing the low boiling point material from the
melt by evaporation so as to increase the polymerization degree of the prepolymer of
the condensation polymer and/or the condensation polymer. Preferable examples
of the condensation polymer include polyesters such as aromatic-aliphatic polyesters
such as polyethylene terephthalate, polytrimethylene terephthalate and polybutylene
25 terephthalate, and various copolyesters, polyesters of hydroxycarboxylic acids such
as glycolic acid and lactic acid, and various copolyesters, aliphatic-aliphatic
26

A0501 UP24_KAN
polyesters between an aliphatic diol and an aliphatic dicarboxylic acid, and various
copolyesters, and aromatic-aromatic polyesters such as polyarylates and liquid
crystal polyesters, and various copolyesters; polyamides such as aliphatic
polyamides such as nylon 6, nylon 66, nylon 612 and nylon 12, and various
5 copolyamides, and aliphatic-aromatic polyamides such as nylon 6T, and various
copolyamides; polycarbonates such as aliphatic polycarbonates, aromatic
polycarbonates, and various copolycarbonates; and polyester polycarbonates. By
using the evaporation apparatus according to the present invention, a high-purity and
high-performance condensation polymer can be produced stably for a prolonged
10 period of time with no discoloration or gelated material or solid foreign material, and
with very little variation in molecular weight.
Alternatively, it is also preferable to use the industrial evaporation apparatus
according to the present invention, in the case that the liquid is a melt of a
thermoplastic polymer A, and the lower boiling point material comprises a monomer,
15 an oligomer, a by-produced material and so on contained in the polymer, as a
purifying apparatus for removing the lower boiling point material from the melt by
evaporation so as to increase the purity of the polymer. Preferable examples of the
thermoplastic polymer A include polystyrene-based polymers such as polystyrene,
high impact polystyrene (HIPS), and various copolymers; polyvinyl chloride-based
20 polymers such as polyvinyl chloride, and various copolymers; polyvinylidene
chloride-based polymers such as polyvinylidene chloride, and various copolymers;
acrylonitrile-based polymers such as AS resins, ABS resins, and various copolymers;
polyolefins such as polypropylene; polyacrylic ester-based polymers; polymethacrylic
ester-based polymers such as PMMA, and various copolymers; and thermoplastic
25 elastomers. According to the evaporation apparatus of the present invention,
impurities such as residual monomers contained in the thermoplastic polymer A can
27

A0501 UP24_KAN
be removed efficiently at a relatively low temperature, and hence a high-purity and
high-performance thermoplastic polymer A can be obtained with no thermal
decomposition and no discoloration.
Alternatively, it is also preferable to use the industrial evaporation apparatus
5 according to the present invention, in the case that the liquid is a solution of a
thermoplastic polymer B, and the lower boiling point material comprises a solvent in
which the thermoplastic polymer is dissolved and/or a monomer, an oligomer, a
by-produced material and so on contained in the polymer solution, as a separation
recovery / purification apparatus for removing the lower boiling point material from
10 the solution by evaporation so as to separate and thus recover the thermoplastic
polymer from the solution and increase the purity of the thermoplastic polymer. A
preferable example of the solution of the thermoplastic polymer B is a solution of a
polymer such as SBR, BR or EPDM produced through solution polymerization using
a solution of an aromatic polycarbonate in a chlorinated solvent (e.g. methylene
15 chloride, chlorobenzene), a solvent (e.g. toluene, hexane), etc. Moreover, it is also
preferable to remove the solvent and so on from an aromatic polycarbonate melt
remaining a chlorinated solvent or an elastomer remaining a polymerization solvent.
According to the evaporation apparatus of the present invention, the solvent and
impurities can be removed efficiently at a relatively low temperature, and hence a
20 high-purity and high-performance thermoplastic polymer B can be obtained with no
thermal decomposition and no discoloration.
The industrial evaporation apparatus according to the present invention is
particularly suitable for removing lower boiling point material by evaporation from a
liquid having a relatively high viscosity. For example, it is particularly suitable for the
25 case of using the industrial evaporation apparatus according to the present invention
as a polymerization apparatus for a condensation polymer. In the case of using the
28

A0501 UP24_KAN
conventional polymerization apparatuses, there have been places where some of the
liquid resides while being heated for a prolonged period of time, whereupon this
liquid undergoes degeneration such as discoloration, gelation, crosslinking,
production of an ultra-high molecular weight polymer, solidification, scorching,
5 carbonization or the like, and hence it is has been impossible to avoid the drawback
of degenerated material mixing in the polymer progressively or suddenly. However,
according to the industrial evaporation apparatus of the present invention, there are
no such drawbacks, and moreover the industrial evaporation apparatus according to
the present invention exhibits excellent effects not exhibited by the conventional
10 polymerization apparatuses.
In other words, in the case, for example, of producing an aromatic
polycarbonate by polymerizing a molten prepolymer obtained from an aromatic
dihydroxy compound and a diaryl carbonate, the reaction temperature must generally
be in a range of from 200 to 350°C, and the viscosity increases dramatically in the
15 latter half of the polymerization in particular. An aromatic monohydroxy compound
produced through an equilibrium reaction must be withdrawn from the
ultra-high-viscosity material, and hence with the conventional polymerization
apparatuses, for example even if a horizontal twin-shaft agitation type
ultra-high-viscosity polymer reactor has been used, it has been necessary to carry
20 out the reaction for a prolonged period of time at a high temperature of not less than
30 0°C and under a high vacuum with a pressure of not more than 133 Pa, and
moreover production of a high molecular weight material for sheets or the like has
been difficult.
However, according to the polymerization apparatus of the present invention,
25 efficient surface renewal occurs naturally accompanying internal stirring, and hence
the polymerization reaction can be carried out at a relatively low temperature. A
29

A0501 UP24_KAN
preferable reaction temperature is thus from 100 to 290°C, more preferably from 150
to 270°C. It is a characteristic feature of the polymerization apparatus according to
the present invention that polymerization can be carried out adequately at a lower
temperature than in the case of the conventional mechanically agitated
5 polymerization apparatus, and this is also one reason why a high-quality aromatic
polycarbonate can be produced with no discoloration or deterioration in properties.
Furthermore, with the conventional polymerization apparatuses, there have been
drawbacks such as contamination with foreign materials, and leaking in of air or the
like through an agitator seal under a high vacuum. However, according to the
10 polymerization apparatus of the present invention, because there is no mechanical
agitation, there is no agitator seal, and hence there is very little leaking in of air or the
like or contamination with foreign materials, which is another reason why a
high-purity and high-performance aromatic polycarbonate can be produced. Such
excellent effects are also achieved with other condensation polymers, in particular
15 polyesters and polyamides. These excellent effects are particularly marked in the
case of producing polyethylene terephthalate, polytrimethylene terephthalate,
polybutylene terephthalate, nylon 6, or nylon 66.
In the case of producing a condensation polymer using the industrial
evaporation apparatus according to the present invention, as the polymerization
20 reaction proceeds, lower boiling point materials by-produced through an equilibrium
reaction are removed from the reaction system, whereby the reaction rate can be
increased. A method in which an inert gas that does not have an adverse effect on
the reaction such as nitrogen, argon, helium, carbon dioxide or a lower hydrocarbon
gas is introduced into the polymerization apparatus, and the lower boiling point
25 materials are entrained by this gas and thus removed, a method in which the
reaction is carried out under a reduced pressure, or the like is thus preferably used.
30

A0501 UP24_KAN
Alternatively, a method in which these two methods are used together can also be
preferably used. In such a case, there is no need to introduce a large amount of the
inert gas into the polymerization apparatus, but rather just enough to maintain an
inert gas atmosphere inside the apparatus is sufficient.
5 The reaction pressure in the case of producing a condensation polymer
using the industrial evaporation apparatus according to the present invention varies
depending on the types of lower boiling point material by-produced, the type and
molecular weight of the polymer to be produced, the polymerization temperature, and
so on, but in the case, for example, of producing an aromatic polycarbonate from a
10 molten prepolymer produced from bisphenol A and diphenyl carbonate, in the case of
a number average molecular weight of not more than 5,000, the reaction pressure is
preferably in a range of from 400 to 3,000 Pa, and in the case of a number average
molecular weight of from 5,000 to 10,000, the reaction pressure is preferably in a
range of from 50 to 500 Pa. In the case of a number average molecular weight
15 equal to or greater than 10,000, the reaction pressure is preferably not more than
300 Pa, particularly preferably in a range of from 20 to 250 Pa.
In the case of producing a condensation polymer using the industrial
evaporation apparatus according to the present invention as a polymerization
apparatus, a polymer having the desired polymerization degree can be produced
20 using only one such evaporation apparatus, but depending on the polymerization
degree of the monomer melt or molten prepolymer used as the starting material, the
amount produced of the polymer, and so on, a system in which a plurality of such
evaporation apparatuses are linked together so that the polymerization degree is
progressively increased may be preferable. In this case, guides and reaction
25 conditions suitable for the polymerization degree of the prepolymer or polymer to be
produced are preferably adopted for each of the evaporation apparatuses individually.
31

A0501 UP24_KAN
For example, in the case of a system in which a first guide-contacting downflow type
polymerization apparatus, a second guide-contacting downflow type polymerization
apparatus, a third guide-contacting downflow type polymerization apparatus, a fourth
guide-contacting downflow type polymerization apparatus and so on are used so that
5 the polymerization degree is progressively increased, taking the total external
surface areas of the guides possessed by the polymerization apparatuses to be S1,
S2, S3, S4 ... respectively, the system can be made to be such that S1 ≥ S2≥
S3 ≤ S4≤ .... Moreover, the polymerization temperature may be the same in
each of the polymerization apparatuses, or alternatively may be progressively
10 increased. The polymerization pressure may also be progressively reduced in the
polymerization apparatuses.
In this sense, in the case, for example, of progressively increasing the
polymerization degree using two polymerization apparatuses, i.e. a first
guide-contacting downflow type polymerization apparatus and a second
15 guide-contacting downflow type polymerization apparatus, it is preferable to use
guides such that the total external surface area S1 (m2) of the guides in the first
polymerization apparatus and the total external surface area S2 (m2) of the guides in
the second polymerization apparatus satisfy the following formula (13):
1 ≤S1 /S2 ≤ 20 (13).
20 If S1 / S2 is less than 1, then problems arise such as variation in the
molecular weight increasing so that prolonged stable production becomes difficult,
and it becoming difficult to obtain a prescribed production amount, whereas if S1 / S2
is greater than 20, then the flow rate of the molten prepolymer flowing down the
guides in the second polymerization apparatus becomes high, and as result
25 problems arise such as the residence time of the molten prepolymer becoming short
so that it becomes difficult to obtain a polymer of the required molecular weight. For
32

A0501 UP24_KAN
such reasons, a more preferable range is 1.5 ≤ S1 / S2 ≤ 15.
According to the industrial evaporation apparatus or polymerization
equipment of the present invention, not less than 1 ton / hr of a concentrated liquid or
polymer can easily be produced. In the case of producing a condensation polymer
5 from a monomer melt or a molten prepolymer, the polymerization is carried out
through an ordinary polymerization reaction while discharging by-produced lower
boiling point materials out of the system, and hence it is necessary for the monomer
melt or molten prepolymer used as the starting material to be fed into the
polymerization apparatus or equipment in an amount greater than 1 ton / hr. The
10 amount of the monomer melt or molten prepolymer constituting the liquid fed into the
evaporation apparatus thus varies depending on the polymerization degree thereof
and the polymerization degree of the polymer to be produced, but is generally from
10 to 500 kg/hr greater than the amount of the polymer produced per 1 ton / hr of the
polymer produced, i.e. in a range of from 1.01 to 1.5 ton / hr per 1 ton / hr of the
15 polymer produced. Moreover, in the case of carrying out concentration through
evaporation or purification through evaporation on a thermoplastic polymer or liquid
containing lower boiling point material, the amount of the liquid fed in varies
depending on the lower boiling point material content and the required concentration
degree or purification degree, but is generally in a range of from 1.001 to 100 ton / hr,
20 preferably from 1.005 to 50 ton / hr, more preferably from 1.01 to 20 ton / hr.
So long as the industrial evaporation apparatus according to the present
invention satisfies the conditions described in the claims, and moreover has a
correspondingly suitable mechanical strength, the industrial evaporation apparatus
may be of any type, and may have adjoined thereto equipment having some other
25 function required for continuous operation. Moreover, according to the industrial
evaporation apparatus of the present invention, a plurality of such industrial
33

A0501 UP24_KAN
evaporation apparatuses may be joined together, and furthermore equipment having
some function other than evaporation may be adjoined thereto.
Examples
5 Next, the present invention will be described in more detail with reference to
Examples and Reference Examples.
[Example 1]:
An industrial evaporation apparatus having a disk-shaped flow path
controlling member 20 of thickness approximately 2 cm and guides 4 as shown in
10 FIGS. 2 and 3. The disk-shaped flow path controlling member 20 was fixed
suspended from the top thereof such that the spacing from the top internal wall 23 of
the liquid feeding zone 3 was approximately 8 cm. Moreover, the spacing between
the internal sidewall surface 22 of the liquid feeding zone 3 and the flow path
controlling member 20 was approximately 9 cm, and the spacing between the
15 perforated plate 2 and the flow path controlling member 20 was approximately 8 cm.
Note that a peripheral portion of the disk-shaped flow path controlling member 20
was designed such that the vertical section thereof was a semicircle of radius
approximately 1 cm, and was thus devised such that the liquid would not stagnate
around this peripheral portion. Moreover, the section of the joint between the
20 internal sidewall surface22 of the liquid feeding zone 3 and the perforated plate 2
was designed to be concave on the inside as shown in FIG. 6, and an angle E for the
rising portion was approximately 170°. The material of the evaporation apparatus
was all stainless steel. The discharging pump 8 is preferably a gear pump in the
case that the concentrated liquid is of high viscosity, and is an ordinary liquid-feeding
25 pump in the case that the viscosity is not so high. The industrial evaporation
apparatus had a cylindrical side-wall casing 10 and a conical bottom-wall casing 11,
34

A0501 UP24_KAN
and was such that L = 1,000 cm, h = 900 cm, D = 500 cm, d = 40 cm, C = 155°, S =
250 m2, A= 19.625 m2, A/ B = 156.25, D /d = 12.5, L/ D = 2, and r = 0.3 cm. All of
the formulae (1) to (12) were satisfied. Care was taken such that, in the liquid
feeding zone 3, the liquid containing lower boiling point materials fed in from the
5 liquid receiving port 1 passes between the upper surface of the flow path controlling
member 20 and the top internal wall 23 of the liquid feeding zone 3, and between the
internal sidewall surface 22 of the liquid feeding zone 3 and the flow path controlling
member 20, and is then distributed uniformly from the holes (e.g. 21) in the
perforated plate 2 to the guides 4 while flowing mainly from the peripheral portion
10 toward the central portion of the perforated plate 2. An inert gas feeding port 9 was
provided in a lower portion of the evaporation apparatus, and an evaporated material
outlet 6 (generally connected to a gas condenser and a pressure-reducing
apparatus) for the lower boiling point materials was provided in an upper portion of
the evaporation apparatus. A jacket or a heating tube for a heating medium was
15 provided on the outside of the evaporation apparatus, so that the evaporation
apparatus could be maintained at a prescribed temperature using the heating
medium.
[Reference Example 1]:
Using the industrial evaporation apparatus of Example 1 as a polymerization
20 apparatus for a condensation polymer, an aromatic polycarbonate was produced. A
molten prepolymer (number average molecular weight Mn = 4,000) for the aromatic
polycarbonate that had been produced from bisphenol A and diphenyl carbonate
(molar ratio of diphenyl carbonate to bisphenol A = 1.05) and was held at 260°C was
continuously fed into the liquid feeding zone 3 from the liquid receiving port 1 by a
25 feed pump. The molten prepolymer, which was continuously fed into the
evaporation zone 5 (polymerization reaction zone) from the holes in the perforated
35

A0501 UP24_KAN
plate 2 while flowing from the peripheral portion toward the central portion of the
perforated plate 2, was subjected to polymerization while flowing down along the
guides 4. The polymerization reaction zone was held at 80 Pa via a vacuum vent 6.
Produced aromatic polycarbonate entering into the bottom portion 11 of the
5 polymerization apparatus from the bottom of the guides 4 was continuously
withdrawn at a flow rate of 5.5 ton / hr from the discharge port 7 by the discharging
pump 8 such that the amount of the aromatic polycarbonate in the bottom portion 11
was constant.
The number average molecular weight Mn of the aromatic polycarbonate
10 withdrawn from an outlet 12 after 50 hours from commencement of operation was
10 ,500, and the aromatic polycarbonate had a good color (b* = 3.2). Moreover, the
tensile elongation was 98%. The values of Mn for the aromatic polycarbonate
withdrawn from the outlet 12 after 60 hours, 100 hours, 500 hours, 1,000 hours,
2,000 hours, 3,000 hours, 4,000 hours, and 5,000 hours from commencement of
15 operation were 10,500, 10,550, 10,500, 10,550, 10,500, 10,500, 10,550, and 10,500
respectively, and hence operation was stable.
The aromatic polycarbonate produced as above had a content of alkali metal
and/or alkaline earth metal compounds of 0.04 to 0.05 ppm in terms of the metallic
elements, which was used as the catalyst.
20
[Example 2]:
Polymerization equipment for a condensation polymerization type polymer in
which two industrial evaporation apparatuses each having a flow path controlling
member 20 and guides 4 as shown in FIGS. 2 and 3 are arranged in series. An
25 aromatic polycarbonate was produced using this polymerization equipment (first
polymerization apparatus plus second polymerization apparatus). The material of
36

A0501 UP24_KAN
the evaporation apparatuses was all stainless steel. The discharging pump 8 for
each of the evaporation apparatuses was a gear pump. The first polymerization
apparatus, which was of a guide-contacting downflow type, had a cylindrical
side-wall casing 10 and a conical bottom-wall casing 11, and was such that L = 950
5 cm, h = 850 cm, D = 400 cm, d = 20 cm, C = 150°, S = 750 m2, A= 12.56 m2, A/ B =
400, D / d = 20, L / D = 2.375, and r = 0.3 cm. Note that the diameter of the cross
section of the flow path controlling member 20 was a little small, but this cross
section had the same shape as in Example 1, and the spacings between the flow
path controlling member 20 and the wall surfaces (23 and 22) of the liquid feeding
10 zone 3 and the spacing between the flow path controlling member 20 and the
perforated plate 2 were as in Example 1. Moreover, as in Example 1, the section of
the joint between the internal sidewall surface 22 of the liquid feeding zone 3 and the
perforated plate 2 was designed to be concave on the inside as shown in FIG. 6, and
an angle E for the rising portion was approximately 170°. The above values satisfy
15 all of the formulae (1) to (12). Moreover, the second polymerization apparatus was
the same as the polymerization apparatus of Example 1.
[Reference Example 2]:
A molten prepolymer (number average molecular weight Mn = 2,500) for an
20 aromatic polycarbonate that had been produced from bisphenol A and diphenyl
carbonate (molar ratio of diphenyl carbonate to bisphenol A = 1.06) and was held at
265°C was continuously fed into the liquid feeding zone 3 from the liquid receiving
port 1 of the first polymerization apparatus by a feed pump. The molten prepolymer,
which was continuously fed into the polymerization reaction zone via the perforated
25 plate 2 in the first polymerization apparatus, was subjected to polymerization while
flowing down along the guides 4. The polymerization reaction zone of the first
37

A0501 UP24_KAN
polymerization apparatus was held at a pressure of 800 Pa via a vacuum vent 6.
Aromatic polycarbonate molten prepolymer of increased polymerization degree
(number average molecular weight Mn = 5,500) entering the bottom portion 11 of the
polymerization apparatus from the bottom of the guides 4 was continuously
5 withdrawn at a constant flow rate from the discharge port 7 by the discharging pump
8 such that the amount of the aromatic polycarbonate molten prepolymer in the
bottom portion 11 was constant. This molten prepolymer was continuously fed into
the liquid feeding zone 3 from the liquid receiving port 1 of the second polymerization
apparatus by a feed pump. The molten prepolymer, which was continuously fed
10 into the polymerization reaction zone via the perforated plate 2 in the second
polymerization apparatus, was subjected to polymerization while flowing down along
the guides 4. The polymerization reaction zone of the second polymerization
apparatus was held at a pressure of 50 Pa via a vacuum vent 6. Produced aromatic
polycarbonate entering the bottom portion 11 of the second polymerization apparatus
15 from the bottom of the guides 4 was continuously withdrawn at a flow rate of 6 ton/hr
from the discharge port 7 by the discharging pump 8 such that the amount of the
aromatic polycarbonate in the bottom portion 11 was constant.
The number average molecular weight Mn of the aromatic polycarbonate
withdrawn from an outlet 12 of the second polymerization apparatus after 50 hours
20 from commencement of operation was 11,500, and the aromatic polycarbonate had a
good color (b* = 3.2). Moreover, the tensile elongation was 99%. The values of
Mn for the aromatic polycarbonate withdrawn from the outlet 12 after 60 hours, 100
hours, 500 hours, 1,000 hours, 2,000 hours, 3,000 hours, 4,000 hours, and 5,000
hours from commencement of operation were 11,500, 11,550, 11,500, 11,550, 11,500,
25 11,500, 11,550, and 11,500 respectively, and hence operation was stable.
The aromatic polycarbonate produced as above had a content of alkali metal
38

A0501 UP24_KAN
and/or alkaline earth metal compounds of 0.03 to 0.05 ppm in terms of the metallic
elements, which was used as the catalyst.
Industrial Applicability
5 The evaporation apparatus according to the present invention is preferably
used as an industrial evaporation apparatus suitable for efficiently concentrating a
large amount of a liquid containing material having a lower boiling point than that of
the liquid, without drawbacks such as discoloration, contamination with foreign
material, or deterioration in properties. It is particularly preferable to use the
10 evaporation apparatus according to the present invention in the case that the liquid
has a relatively high viscosity. Particularly preferable applications of the industrial
evaporation apparatus according to the present invention are as a condensation
polymer polymerization apparatus, a purifying apparatus for a thermoplastic polymer
melt, or an apparatus for separating and thus recovering the polymer from a
15 thermoplastic polymer solution and purifying the polymer.
39

A0501 UP24_KAN
CLAIMS
We claim:
1. An industrial evaporation apparatus in which a liquid containing a
material having a lower boiling point than that of said liquid is made to flow down
5 along an external surface of a guide that does not themselves have a heat source,
during which time said lower boiling point material is evaporated, wherein
improvement comprises:
(1) said evaporation apparatus comprising a liquid receiving port; a liquid
feeding zone for feeding said liquid via a perforated plate to said guide provided in
10 an evaporation zone; said evaporation zone having a plurality of guides that extend
downward within a space enclosed by said perforated plate, a side-wall casing, and
a bottom-wall casing; an evaporated material outlet provided in said evaporation
zone; and a liquid discharge port provided in a lowermost portion of the bottom-wall
casing;
15 (2) a flow path controlling member which has a function of making said liquid
fed onto the perforated plate from said liquid receiving port flow mainly from a
peripheral portion toward a middle portion of the perforated plate being provided in
said liquid feeding zone;
(3) an internal sectional area A (m2) taken through a horizontal plane of the
20 side-wall casing of said evaporation zone satisfying the following formula (1):
0.7≤ A ≤300 (1);
(4) a ratio between said A (m2) and an internal sectional area B (m2) taken
through a horizontal plane of the liquid discharge port satisfying the following formula
(2):
25 20 ≤ A/B ≤1000 (2);
(5) the bottom-wall casing constituting the bottom portion of said evaporation
40

A0501 UP24_KAN
zone being connected at an internal angle C (°) to said side-wall casing on said
bottom-wall casing, wherein said angle C (°) satisfies the following formula (3):
110≤C≤165 (3);
(6) a length h (cm) of each of said guides satisfying the following formula (4):
5 150≤ h≤ 5000 (4);
(7) a total external surface area S (m2) of said guides satisfying the following
formula (5):
2 ≤ S ≤50000 (5).
10 2. The industrial evaporation apparatus according to claim 1, wherein not
less than 1 ton / hr of said liquid is subjected to the evaporation.
3. The industrial evaporation apparatus according to claim 1 or 2, wherein
an angle E (°) between an internal sidewall surface of said liquid feeding zone and
15 said perforated plate satisfies the following formula (6):
100≤ E 4. The industrial evaporation apparatus according to any one of claims 1 to
3, wherein said side-wall casing of said evaporation zone is cylindrical with an inside
20 diameter D (cm) and a length L (cm), the bottom-wall casing connected at a bottom
portion of said side-wall casing is conical, and the liquid discharge port, which is in
the lowermost portion of the conical bottom-wall casing, is cylindrical with an inside
diameter d (cm), wherein D, L and d satisfy the following formulae (7), (8), (9) and
(10):
25 100 ≤ D≤1800 (7)
5≤ D/d ≤ 50 (8)
41

A0501 UP24_KAN
0.5 ≤ L/D≤30 (9)
h-20≤ L ≤ h + 300 (10).
5. The industrial evaporation apparatus according to any one of claims 1 to
5 4, wherein the h satisfies the following formula (11):
400 6. The industrial evaporation apparatus according to any one of claims 1 to
5 , wherein one of said guides is cylindrical, or pipe-shaped and made to be such that
10 the liquid and/or gaseous material cannot enter therein, with an outside diameter r
(cm), wherein r satisfies the following formula (12):
0.1 ≤ r≤1 (12).
7. The industrial evaporation apparatus according to any one of claims 1 to
15 5, wherein said guides comprise guides according to claim 6, and the guides are
joined together by transverse supports.
8. The industrial evaporation apparatus according to any one of claims 1 to
5 , wherein said guides comprise guides according to claim 6, and form one of a
20 grid-like or mesh-like guide structure in which the guides are fixed together by
transverse supports, a three-dimensional guide structure in which a plurality of
grid-like or mesh-like guide structures are arranged in front of and behind one
another and are fixed together by transverse supports, and a jungle-gym-like
three-dimensional guide structure in which the guides are fixed together in front of
25 and behind, and left and right of, one another by transverse supports.
42

A0501 UP24_KAN
9. The industrial evaporation apparatus according to any one of claims 1 to
8, wherein said liquid is a melt of a monomer or a mixture of two or more kinds of
monomers for producing a condensation polymer, and/or a prepolymer of the
condensation polymer, and/or the condensation polymer, the lower boiling point
5 material is a by-produced material and/or oligomer produced through condensation
polymerization, and said industrial evaporation apparatus is a condensation polymer
polymerization apparatus for removing said lower boiling point material from said
melt by evaporation so as to increase a polymerization degree of the prepolymer of
the condensation polymer and/or the condensation polymer.
10
10. The industrial evaporation apparatus according to claim 9, wherein the
condensation polymer is a polyester, a polyamide, or a polycarbonate.
11. The industrial evaporation apparatus according to any one of claims 1
15 to 8, wherein said liquid is a melt of a thermoplastic polymer A, said lower boiling
point material is a monomer, an oligomer, and a by-produced material contained in
the polymer, and the industrial evaporation apparatus is a purifying apparatus for
removing said lower boiling point material from said melt by evaporation so as to
increase purity of said thermoplastic polymer A.
2012. The industrial evaporation apparatus according to claim 11, wherein
said thermoplastic polymer A is a polystyrene-based polymer, a polyvinyl
chloride-based polymer, a polyvinylidene chloride-based polymer, a
polyacrylonitrile-based polymer, a polyacrylic ester-based polymer, a polymethacrylic
25 ester-based polymer, or a thermoplastic elastomer.
43

It is an object of the present invention, in the case of an apparatus in which a liquid containing material having a lower boiling point than that of the liquid is made to flow down along an external surface of a guide, during which time the lower boiling point material is evaporated, to provide a specific apparatus that can be operated stably for a prolonged period of time on an industrial scale such that not less than 1 ton/hr of the liquid is subjected to the evaporation, and furthermore to provide a specific industrial evaporation apparatus in which there are no problems due to degeneration caused by some of the liquid residing in the apparatus for a prolonged period of time. The present inventors have reached to the present invention upon discovering that the above object can be attained, and a high-quality and high-purity concentrated liquid or condensation polymer or thermoplastic polymer can easily be obtained, by using an industrial evaporation apparatus having a specified structure in which there are guides that do not themselves have a heat source, a flow path controlling member having a function of making the liquid fed onto a perforated plate from a liquid receiving port flow mainly from a peripheral portion toward a central portion of the perforated plate is provided in a liquid feeding zone, and formulae (1) to (5), or formulae (1) to (10), or formulae (1) to (12), are satisfied.

Documents:

01490-kolnp-2007-abstract.pdf

01490-kolnp-2007-claims.pdf

01490-kolnp-2007-correspondence others 1.1.pdf

01490-kolnp-2007-correspondence others 1.2.pdf

01490-kolnp-2007-correspondence others 1.3.pdf

01490-kolnp-2007-correspondence others 1.4.pdf

01490-kolnp-2007-correspondence others.pdf

01490-kolnp-2007-description complete.pdf

01490-kolnp-2007-drawings.pdf

01490-kolnp-2007-form 1.pdf

01490-kolnp-2007-form 18.pdf

01490-kolnp-2007-form 2.pdf

01490-kolnp-2007-form 3.pdf

01490-kolnp-2007-form 5.pdf

01490-kolnp-2007-gpa.pdf

01490-kolnp-2007-international publication.pdf

01490-kolnp-2007-international search report.pdf

01490-kolnp-2007-pct others.pdf

01490-kolnp-2007-pct request.pdf

01490-kolnp-2007-priority document 1.1.pdf

01490-kolnp-2007-priority document.pdf

1490-KOLNP-2007-(10-09-2012)-AMANDED CLAIMS.pdf

1490-KOLNP-2007-(10-09-2012)-ANNEXURE TO FORM 3.pdf

1490-KOLNP-2007-(10-09-2012)-CORRESPONDENCE.pdf

1490-KOLNP-2007-(10-09-2012)-DESCRIPTION (COMPLETE).pdf

1490-KOLNP-2007-(10-09-2012)-DRAWINGS.pdf

1490-KOLNP-2007-(10-09-2012)-FORM-1.pdf

1490-KOLNP-2007-(10-09-2012)-FORM-2.pdf

1490-KOLNP-2007-(10-09-2012)-OTHERS.pdf

1490-KOLNP-2007-(11-06-2012)-ABSTRACT.pdf

1490-KOLNP-2007-(11-06-2012)-AMANDED CLAIMS.pdf

1490-KOLNP-2007-(11-06-2012)-DESCRIPTION (COMPLETE).pdf

1490-KOLNP-2007-(11-06-2012)-DRAWINGS.pdf

1490-KOLNP-2007-(11-06-2012)-EXAMINATION REPORT REPLY RECEIVED.pdf

1490-KOLNP-2007-(11-06-2012)-FORM-1.pdf

1490-KOLNP-2007-(11-06-2012)-FORM-2.pdf

1490-KOLNP-2007-(11-06-2012)-FORM-3.pdf

1490-KOLNP-2007-(11-06-2012)-FORM-5.pdf

1490-KOLNP-2007-(11-06-2012)-OTHERS.pdf

1490-KOLNP-2007-(12-06-2012)-PETITION UNDER RULE 137.pdf

1490-KOLNP-2007-CORRESPONDENCE 1.1.pdf

abstract-01490-kolnp-2007.jpg


Patent Number 254447
Indian Patent Application Number 1490/KOLNP/2007
PG Journal Number 45/2012
Publication Date 09-Nov-2012
Grant Date 05-Nov-2012
Date of Filing 26-Apr-2007
Name of Patentee ASAHI KASEI CHEMICALS CORPORATION
Applicant Address 1-2 YURAKU-CHO 1-CHOME, CHIYODA-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 SHINSUKE FUKUOKA 1-2 YURAKU-CHO 1-CHOME, CHIYODA-KU, TOKYO, 100-8440
2 KAZUHIKO MATSUZAKI 1-2 YURAKU-CHO 1-CHOME, CHIYODA-KU, TOKYO, 100-8440
3 HIROSHI HACHIYA 1-2 YURAKU-CHO 1-CHOME, CHIYODA-KU, TOKYO, 100-8440
PCT International Classification Number B01D 1/00
PCT International Application Number PCT/JP2005/021860
PCT International Filing date 2005-11-29
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2004-362739 2004-12-15 Japan