U.S. patent application number 12/662433 was filed with the patent office on 2010-09-09 for polyisocyanate production method and polyisocyanate production system.
This patent application is currently assigned to Mitsui Chemicals Polyurethanes, Inc.. Invention is credited to Fumiaki Hirata, Tsugio Imaizumi, Kouji Maeba, Takao Naito, Takuya Saeki, Masato Saruwatari, Masaaki Sasaki, Hirofumi Takahashi, Kouichirou Terada, Takashi Yamaguchi.
Application Number | 20100226833 12/662433 |
Document ID | / |
Family ID | 36953355 |
Filed Date | 2010-09-09 |
United States Patent
Application |
20100226833 |
Kind Code |
A1 |
Sasaki; Masaaki ; et
al. |
September 9, 2010 |
Polyisocyanate production method and polyisocyanate production
system
Abstract
A polyisocyanate production method that can allow effective use
of hydrogen chloride produced secondarily in a polyisocyanate
production process, while allowing reduction of environmental
burdens, and a polyisocyanate production system for performing the
polyisocyanate production method. After chlorine is allowed to
react with carbon monoxide to produce carbonyl chloride in a
carbonyl chloride producing reactor, the carbonyl chloride produced
in the carbonyl chloride producing reactor is allowed to react with
polyamine in an isocyanate producing reactor to produce
polyisocyanate. Then, after hydrochloric gas produced secondarily
in the isocyanate producing reactor is purified in a hydrogen
chloride purifying column, the purified hydrochloric gas is
oxidized in a hydrogen chloride oxidizing reactor to produce
chlorine. Thereafter, the chlorine thus produced is supplied to the
carbonyl chloride producing reactor from a chlorine resupply line,
so that it is allowed to react with carbon monoxide to produce
carbonyl chloride.
Inventors: |
Sasaki; Masaaki;
(Kamisu-shi, JP) ; Naito; Takao; (Kamisu-shi,
JP) ; Hirata; Fumiaki; (Sodegaura-shi, JP) ;
Saruwatari; Masato; (Omuta-shi, JP) ; Takahashi;
Hirofumi; (Kamisu-shi, JP) ; Maeba; Kouji;
(Kamisu-shi, JP) ; Imaizumi; Tsugio; (Kamisu-shi,
JP) ; Saeki; Takuya; (Omuta-shi, JP) ;
Yamaguchi; Takashi; (Omuta-shi, JP) ; Terada;
Kouichirou; (Omuta-shi, JP) |
Correspondence
Address: |
BUCHANAN, INGERSOLL & ROONEY PC
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Assignee: |
Mitsui Chemicals Polyurethanes,
Inc.
Minato-ku
JP
|
Family ID: |
36953355 |
Appl. No.: |
12/662433 |
Filed: |
April 16, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11597757 |
Nov 28, 2006 |
|
|
|
PCT/JP2006/304447 |
Mar 8, 2006 |
|
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12662433 |
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Current U.S.
Class: |
422/620 ;
422/630 |
Current CPC
Class: |
B01J 2208/00274
20130101; C07C 263/10 20130101; B01J 2219/0011 20130101; B01J
2219/00103 20130101; B01J 2208/00646 20130101; B01J 2208/00716
20130101; B01J 2208/00283 20130101; B01J 2219/00108 20130101; B01J
8/0453 20130101; B01J 2219/0004 20130101; B01J 2208/00265 20130101;
B01J 2219/00105 20130101; B01J 2208/00256 20130101; C07C 265/14
20130101; C07C 263/10 20130101 |
Class at
Publication: |
422/189 |
International
Class: |
B01J 19/00 20060101
B01J019/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 10, 2005 |
JP |
2005-068263 |
Mar 10, 2005 |
JP |
2005-068264 |
Claims
1. A polyisocyanate production system comprising, a carbonyl
chloride production unit for producing carbonyl chloride by
allowing chlorine to react with carbon monoxide, a polyisocyanate
production unit for producing polyisocyanate by allowing the
carbonyl chloride produced in the carbonyl chloride production unit
to react with polyamine, a chlorine production unit for producing
chlorine by oxidizing hydrogen chloride produced secondarily in the
polyisocyanate production unit, and a chlorine resupply unit for
supplying the chlorine produced in the chlorine production unit to
the carbonyl chloride production unit, to allow the chlorine to
react with carbon monoxide in the carbonyl chloride production unit
to produce carbonyl chloride.
2. A polyisocyanate production system comprising, a polyamine
production unit for producing polymethylene polyphenylene polyamine
by allowing aniline to react with formaldehyde, using an acid
catalyst containing hydrochloric acid, a carbonyl chloride
production unit for producing carbonyl chloride by allowing
chlorine to react with carbon monoxide, a polyisocyanate production
unit for producing polymethylene polyphenylene polyisocyanate by
allowing the carbonyl chloride produced in the carbonyl chloride
production unit to react with polymethylene polyphenylene polyamine
produced in the polyamine production unit, a chlorine production
unit for producing chlorine by oxidizing hydrogen chloride produced
secondarily in the polyisocyanate production unit, a hydrochloric
acid production unit for producing hydrochloric acid by allowing at
least a part of the hydrogen chloride produced secondarily in the
polyisocyanate production unit and/or unoxidized hydrogen chloride
in the chlorine production unit to be absorbed or mixed in water, a
chlorine resupply unit for supplying the chlorine produced in the
chlorine production unit to the carbonyl chloride production unit,
to allow the chlorine to react with carbon monoxide in the carbonyl
chloride production unit to produce carbonyl chloride, and a
hydrochloric acid resupply unit for supplying the hydrochloric acid
produced in the hydrochloric acid production unit to the polyamine
production unit, to use the hydrochloric acid as the acid catalyst
in the polyamine production unit.
3. A polyisocyanate production system comprising, a carbonyl
chloride production unit for producing carbonyl chloride by
allowing chlorine to react with carbon monoxide, a polyisocyanate
production unit for producing tolylene diisocyanate by allowing the
carbonyl chloride produced in the carbonyl chloride production unit
to react with tolylene diamine, a chlorine production unit for
producing chlorine by oxidizing hydrogen chloride produced
secondarily in the polyisocyanate production unit, a hydrochloric
acid production unit for producing hydrochloric acid by allowing at
least a part of the hydrogen chloride produced secondarily in the
polyisocyanate production unit and/or unoxidized hydrogen chloride
in the chlorine production unit to be absorbed or mixed in water,
and a chlorine resupply unit for supplying the chlorine produced in
the chlorine production unit to the carbonyl chloride production
unit, to allow the chlorine to react with carbon monoxide in the
carbonyl chloride production unit to produce carbonyl chloride.
4. A polyisocyanate production system comprising, a nitration
reactor for nitrating an aromatic raw material, using sulfuric acid
and nitric acid, to introduce a nitro group in an aromatic ring of
the aromatic raw material, a polyamine producing reactor for
producing polyamine by reducing the nitro group introduced in the
aromatic ring of the aromatic raw material in the nitration reactor
to an amino group, a carbonyl chloride producing reactor for
producing carbonyl chloride by allowing chlorine to react with
carbon monoxide, a polyisocyanate producing reactor for producing
polyisocyanate by allowing the carbonyl chloride produced in the
carbonyl chloride producing reactor to react with the polyamine
produced in the polyamine producing reactor, a hydrogen chloride
oxidizing reactor for oxidizing hydrogen chloride produced
secondarily in the polyisocyanate producing reactor to produce a
mixture of chlorine and water, a dehydration column for dehydrating
the mixture produced in the hydrogen chloride oxidizing reactor by
putting the mixture into contact with, sulfuric acid, thereby to
produce chlorine, and a sulfuric acid supply line for supplying the
sulfuric acid used in the dehydration column from the dehydration
column to the nitration reactor so that the sulfuric acid can be
reused in the nitration process.
5. The polyisocyanate production system according to claim 4, which
further comprises a chlorine supply line for supplying the chlorine
produced in the dehydration column from the dehydration column to
the carbonyl chloride producing reactor so that the chlorine is
allowed to react with carbon monoxide to produce carbonyl chloride
in the carbonyl chloride producing reactor.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a divisional application of
pending U.S. patent application Ser. No. 11/597,757, filed Nov. 28,
2006, which, in turn, is the National Stage Application under
.sctn.371 of International Application No. PCT/JP2006/304447, filed
Mar. 8, 2006, which claims priority from Japanese Application Nos.
2005-068263 and 2005-068264, each filed Mar. 10, 2005, the entire
disclosure of each of which is incorporated herein by
reference.
TECHNICAL FIELD
[0002] The present invention relates to a polyisocyanate production
method for producing polyisocyanate used as a raw material of
polyurethane, and to a polyisocyanate production system for
performing the polyisocyanate production method.
BACKGROUND ART
[0003] Polyisocyanate used as a raw material of polyurethane is
industrially produced by allowing carbonyl chloride to react with
polyamine for isocyanate reaction.
[0004] In this isocyanate reaction, corresponding polyisocyanate is
produced from polyamine and a large quantity of hydrochloric gas is
produced secondarily.
[0005] The hydrochloric gas produced secondarily is used for
oxychlorination in production of vinyl chloride, for example.
[0006] Further, a production method for producing chlorine
industrially by oxidizing the hydrochloric gas produced secondarily
has been proposed (cf. Patent Document 1 and Patent Document 2, for
example).
[0007] When hydrochloric gas is oxidized, water is also produced
secondarily together with chlorine. The mixture of chlorine and
water thus produced is dehydrated using a sulfuric acid to dry the
chlorine, as is known (cf. Patent Document 3, for example).
[0008] Patent Document 1: Japanese Unexamined Patent Publication
No. 62-275001,
[0009] Patent Document 2: Japanese Unexamined Patent Publication
No. 2000-272906, and
[0010] Patent Document 3: Japanese Unexamined Patent Publication
No. 2004-217455.
DISCLOSURE OF THE INVENTION
Problem to be Solved by the Invention
[0011] However, when production equipment of vinyl chloride is not
located adjacent to production equipment of polyisocyanate, the
hydrochloric gas produced secondarily in the isocyanate reaction
cannot be utilized for oxychlorination in the production of the
vinyl chloride.
[0012] When there is a user of chlorine in the same complex or
production facility, the chlorine produced by oxidizing the
hydrochloric gas produced secondarily can be used or sold for other
application. It, however, requires an adjustment of an amount of
polyisocyanate produced and an adjustment of an amount of chlorine
produced in order to make a balance against other products, and
also requires facilities, such as unused hydrogen chloride
discharging equipment, costly high-pressure equipment for chlorine
storage, and low-temperature equipment containing coolant. When
there is no user of chlorine in the same complex or production
facility, delivery equipment is also required in addition to the
costly chlorine storage equipment. Under the circumstances, a
production method for allowing use and consumption of the chlorine
in the same complex or in the same location of production
facilities is being desired.
[0013] When the hydrochloric gas produced secondarily is oxidized,
chlorine and water are produced secondarily. When the mixture of
chlorine and water thus produced is dehydrated using sulfuric acid,
dried chlorine is obtained. On the other hand, since the sulfuric
acid used in the drying absorbs water, a concentration of the
sulfuric acid decreases.
[0014] It is desirable for improvement in dehydration efficiency
that the concentration of sulfuric acid used for the dehydration is
as high as not less than 97 weight %, for example. However, when
the sulfuric acid is tried to be condensed to such a high
concentration for the recycle use, a condensation process is
additionally required, then causing cost rise. On the other hand,
when the sulfuric acid used in the drying is disposed without being
recycled, the sulfuric acid consumption increases, then still
causing inevitable cost rise.
[0015] It is an object of the present invention to provide a
polyisocyanate production method that can allow effective use of
the hydrogen chloride produced secondarily in the polyisocyanate
production process and can also allow reduction of environmental
burdens, and to provide a polyisocyanate production system for
performing the polyisocyanate production method.
[0016] It is another object of the present invention to provide a
polyisocyanate production method that can make effective use of
sulfuric acid used in the dehydration process to reduce production
costs of polyisocyanate, and to provide a polyisocyanate production
system for performing the polyisocyanate production method.
Means for Solving the Problem
[0017] To accomplish the objects described above, the present
invention provides a polyisocyanate production method comprising a
carbonyl chloride production process of producing carbonyl chloride
by allowing chlorine to react with carbon monoxide, a
polyisocyanate production process of producing polyisocyanate by
allowing the carbonyl chloride produced in the carbonyl chloride
production process to react with polyamine, and a chlorine
production process of producing chlorine by oxidizing hydrogen
chloride produced secondarily in the polyisocyanate production
process, wherein the carbonyl chloride is produced by allowing the
chlorine produced in the chlorine production process to react with
carbon monoxide in the carbonyl chloride production process.
[0018] It is preferable that the polyisocyanate production method
of the present invention further comprises a hydrochloric acid
production process of producing the hydrochloric acid by allowing
at least a part of the hydrogen chloride produced secondarily in
the polyisocyanate production process and/or unoxidized hydrogen
chloride in the chlorine production process to be absorbed or mixed
in water.
[0019] In the polyisocyanate production method of the present
invention, it is preferable that in the carbonyl chloride
production process, corresponding to an amount of hydrogen chloride
required for the hydrochloric acid produced in the hydrochloric
acid production process, chlorine is additionally supplied together
with the chlorine produced in the chlorine production process.
[0020] In the polyisocyanate production method of the present
invention, it is preferable that at least a part of the carbonyl
chloride produced in the carbonyl chloride production process is
put in a liquefied state and/or a solution state before the
reaction with polyamine.
[0021] The present invention provides a polyisocyanate production
method comprising a polyamine production process of producing
polymethylene polyphenylene polyamine by allowing aniline to react
with formaldehyde, using acid catalyst containing hydrochloric
acid, a carbonyl chloride production process of producing carbonyl
chloride by allowing chlorine to react with carbon monoxide, a
polyisocyanate production process of producing polymethylene
polyphenylene polyisocyanate by allowing the carbonyl chloride
produced in the carbonyl chloride production process to react with
polymethylene polyphenylene polyamine produced in the polyamine
production process, a chlorine production process of producing
chlorine by oxidizing hydrogen chloride produced secondarily in the
polyisocyanate production process, and a hydrochloric acid
production process of producing the hydrochloric acid by allowing
at least a part of the hydrogen chloride produced secondarily in
the polyisocyanate production process and/or unoxidized hydrogen
chloride in the chlorine production process to be absorbed or mixed
in water, wherein the chlorine produced in the chlorine production
process is allowed to react with carbon monoxide in the carbonyl
chloride production process to produce carbonyl chloride, and the
hydrochloric acid produced in the hydrochloric acid production
process is used as the acid catalyst in the polyamine production
process.
[0022] The present invention provides a polyisocyanate production
method comprising a carbonyl chloride production process of
producing carbonyl chloride by allowing chlorine to react with
carbon monoxide, a polyisocyanate production process of producing
tolylene diisocyanate by allowing the carbonyl chloride produced in
the carbonyl chloride production process to react with tolylene
diamine, a chlorine production process of producing chlorine by
oxidizing hydrogen chloride produced secondarily in the
polyisocyanate production process, a hydrochloric acid production
process of producing the hydrochloric acid by allowing at least a
part of the hydrogen chloride produced secondarily in the
polyisocyanate production process and/or unoxidized hydrogen
chloride in the chlorine production process to be absorbed or mixed
in water, wherein the chlorine produced in the chlorine production
process is allowed to react with carbon monoxide in the carbonyl
chloride production process to produce carbonyl chloride.
[0023] Further, the present invention provides a polyisocyanate
production system comprising a carbonyl chloride production unit
for producing carbonyl chloride by allowing chlorine to react with
carbon monoxide, a polyisocyanate production unit for producing
polyisocyanate by allowing the carbonyl chloride produced in the
carbonyl chloride production unit to react with polyamine, a
chlorine production unit for producing chlorine by oxidizing
hydrogen chloride produced secondarily in the polyisocyanate
production unit, and a chlorine resupply unit for resupplying the
chlorine produced in the chlorine production unit to the carbonyl
chloride production unit, to allow the chlorine to react with
carbon monoxide in the carbonyl chloride production unit to produce
carbonyl chloride.
[0024] The present invention provides a polyisocyanate production
system comprising a polyamine production unit for producing
polymethylene polyphenylene polyamine by allowing aniline to react
with formaldehyde, using acid catalyst containing hydrochloric
acid, a carbonyl chloride production unit for producing carbonyl
chloride by allowing chlorine to react with carbon monoxide, a
polyisocyanate production unit for producing polymethylene
polyphenylene polyisocyanate by allowing the carbonyl chloride
produced in the carbonyl chloride production unit to react with the
polymethylene polyphenylene polyamine produced in the polyamine
production unit, a chlorine production unit for producing chlorine
by oxidizing hydrogen chloride produced secondarily in the
polyisocyanate production unit, a hydrochloric acid production unit
for producing the hydrochloric acid by allowing at least a part of
hydrogen chloride produced secondarily in the polyisocyanate
production unit and/or unoxidized hydrogen chloride in the chlorine
production unit to be absorbed or mixed in water, a chlorine
resupply unit for resupplying the chlorine produced in the chlorine
production unit to the carbonyl chloride production unit, to allow
the chlorine to react with carbon monoxide in the carbonyl chloride
production unit to produce carbonyl chloride, and a hydrochloric
acid resupply unit for resupplying the hydrochloric acid produced
in the hydrochloric acid production unit to the polyamine
production unit, to use the hydrochloric acid as the acid catalyst
in the polyamine production unit.
[0025] The present invention provides a polyisocyanate production
system comprising a carbonyl chloride production unit for producing
carbonyl chloride by allowing chlorine to react with carbon
monoxide, a polyisocyanate production unit for producing tolylene
diisocyanate by allowing the carbonyl chloride produced in the
carbonyl chloride production unit to react with tolylene diamine, a
chlorine production unit for producing chlorine by oxidizing
hydrogen chloride produced secondarily in the polyisocyanate
production unit, a hydrochloric acid production unit for producing
the hydrochloric acid by allowing at least a part of the hydrogen
chloride produced secondarily in the polyisocyanate production unit
and/or unoxidized hydrogen chloride in the chlorine production unit
to be absorbed or mixed in water, and a chlorine resupply unit for
resupplying the chlorine produced in the chlorine production unit
to the carbonyl chloride production unit, to allow the chlorine to
react with carbon monoxide in the carbonyl chloride production unit
to produce carbonyl chloride.
[0026] Further, the present invention provides a polyisocyanate
production method comprising a carbonyl chloride production process
of producing carbonyl chloride by allowing chlorine to react with
carbon monoxide, a polyisocyanate production process of producing
polyisocyanate by allowing the carbonyl chloride produced in the
carbonyl chloride production process to react with polyamine, and a
chlorine production process of producing chlorine to be used in the
carbonyl chloride production process by oxidizing hydrogen chloride
produced secondarily in the polyisocyanate production process,
wherein a start-up operation is first performed by starting
production of carbonyl chloride in the chlorine production process,
starting production of polyisocyanate in the polyisocyanate
production process, and starting production of chlorine in the
chlorine production process, then a load-up operation, in which any
one of the processes, i.e., the process of increasing an amount of
carbonyl chloride produced in the carbonyl chloride production
process, the process of increasing an amount of polyisocyanate
produced in the polyisocyanate production process, and the process
of increasing an amount of chlorine produced in the chlorine
production process, is selectively performed, and then the two
other processes are performed is repeatedly performed until an
amount of polyisocyanate produced reaches a predetermined
amount.
[0027] According to the polyisocyanate production method of the
present invention, since the chlorine to be used in the carbonyl
chloride production process is produced in the chlorine production
process by oxidizing the hydrogen chloride produced secondarily in
the polyisocyanate production process, the chlorine produced can be
allowed to react with carbon monoxide in the carbonyl chloride
production process thereby to produce carbonyl chloride. This means
that the chlorine can be produced from the hydrogen chloride
produced secondarily, and then the chlorine can be reused as the
raw material of the carbonyl chloride. This can allow the recycle
use of chlorine without being drained to the outside of a system,
which can allow efficient use of the hydrogen chloride produced
secondarily, while allowing reduction of environmental burdens.
[0028] Further, in this method, Cl atoms circulate in the system
and a predetermined amount of polyisocyanate is constantly
produced. This requires that the start-up operation at the starting
of the operation and the load-up operation from the starting of the
operation until the predetermined amount of polyisocyanate being
constantly produced are performed effectively.
[0029] In this method, the start-up operation is first performed by
starting production of carbonyl chloride in the chlorine production
process, starting production of polyisocyanate in the
polyisocyanate production process, and starting production of
chlorine in the chlorine production process, then the load-up
operation, in which any one of the processes, i.e., the process of
increasing an amount of carbonyl chloride produced in the carbonyl
chloride production process, the process of increasing an amount of
polyisocyanate produced in the polyisocyanate production process,
and the process of increasing an amount of chlorine produced in the
chlorine production process, is selectively performed, and then the
two other processes are performed, is repeatedly performed until an
amount of polyisocyanate produced reaches a predetermined amount.
This can realized an effective operation by increasing the amount
of polyisocyanate produced in each process overall and stepwise
until the amount of polyisocyanate produced reaches a predetermined
amount.
[0030] According to the polyisocyanate production method of the
present invention, this can allow effective use of the hydrogen
chloride produced secondarily in the polyisocyanate production
process, while allowing reduction of environmental burdens.
Further, this can also realize the effective operation by
increasing the amount of polyisocyanate produced in each process
overall and stepwise until the amount of polyisocyanate produced
reaches a predetermined amount.
[0031] In the polyisocyanate production method of the present
invention, it is preferable that in the start-up operation, after
the production of the carbonyl chloride starts in the carbonyl
chloride production process, the production of polyisocyanate
starts in the polyisocyanate production process and then the
production of chlorine starts in the chlorine production
process.
[0032] In the polyisocyanate production method of the present
invention, it is preferable that in the load-up operation, after an
amount of carbonyl chloride produced is increased in the carbonyl
chloride production process, an amount of polyisocyanate produced
is increased in the polyisocyanate production process and then an
amount of chlorine produced is increased in the chlorine production
process.
[0033] In the polyisocyanate production method of the present
invention, it is preferable that in the chlorine production
process, the hydrogen chloride is oxidized in a fluid bed reactor,
and that in the start-up operation, a warming-up operation of the
fluid bed reactor is performed before the production of chlorine
starts in the chlorine production process.
[0034] In the polyisocyanate production method of the present
invention, it is preferable that in the chlorine production
process, the hydrogen chloride is oxidized in a fixed bed reactor,
and that in the start-up operation, a warming-up operation of the
fixed bed reactor is performed before the production of chlorine
starts in the chlorine production process.
[0035] The present invention provides a polyisocyanate production
method comprising a carbonyl chloride production process of
producing carbonyl chloride by allowing chlorine to react with
carbon monoxide, a polyisocyanate production process of producing
polyisocyanate by allowing the carbonyl chloride produced in the
carbonyl chloride production process to react with polyamine, and a
chlorine production process of producing chlorine to be used in the
carbonyl chloride production process by oxidizing hydrogen chloride
produced secondarily in the polyisocyanate production process,
wherein a start-up operation, in which after chlorine of raw
material previously prepared and carbon monoxide are allowed to
react with each other in the carbonyl chloride production process
to produce carbonyl chloride, the carbonyl chloride produced is
allowed to react with polyamine in the polyisocyanate production
process to produce polyisocyanate and then the hydrogen chloride
produced secondarily is oxidized in the chlorine production process
to produce chlorine to be used in the carbonyl chloride production
process, is first performed, and then a load-up operation, in which
after the chlorine of raw material and the chlorine produced in the
chlorine production process are allowed to react with carbon
monoxide in the carbonyl chloride production process to produce
carbonyl chloride, the carbonyl chloride produced is allowed to
react with polyamine in the polyisocyanate production process to
produce polyisocyanate and then the hydrogen chloride produced
secondarily is oxidized in the chlorine production process to
produce chlorine to be used in the carbonyl chloride production
process, is repeatedly performed until an amount of polyisocyanate
produced reaches a predetermined amount.
[0036] According to the polyisocyanate production method of the
present invention, since the chlorine to be used in the carbonyl
chloride production process is produced in the chlorine production
process by oxidizing the hydrogen chloride produced secondarily in
the polyisocyanate production process, the chlorine produced can be
allowed to react with carbon monoxide in the carbonyl chloride
production process thereby to produce carbonyl chloride. This means
that the chlorine can be produced from the hydrogen chloride
produced secondarily, and then the chlorine can be reused as the
raw material of the carbonyl chloride. This can allow the recycle
use of chlorine without being drained to the outside of the system,
which can allow efficient use of the hydrogen chloride produced
secondarily, while allowing reduction of environmental burdens.
[0037] In this method, Cl atoms circulate in the system and a
predetermined amount of polyisocyanate produced is constantly
produced. This requires that the start-up operation at the starting
of the operation and the load-up operation from the starting of the
operation until the predetermined amount of polyisocyanate being
constantly produced are performed effectively.
[0038] In this method, the start-up operation, in which after
chlorine of raw material previously prepared and carbon monoxide
are allowed to react with each other in the carbonyl chloride
production process to produce carbonyl chloride, the carbonyl
chloride produced is allowed to react with polyamine in the
polyisocyanate production process to produce polyisocyanate and
then the hydrogen chloride produced secondarily is oxidized in the
chlorine production process to produce chlorine to be used in the
carbonyl chloride production process, is first performed. Then, a
load-up operation, in which after the chlorine of raw material and
the chlorine produced in the chlorine production process are
allowed to react with carbon monoxide in the carbonyl chloride
production process to produce carbonyl chloride, the carbonyl
chloride produced is allowed to react with polyamine in the
polyisocyanate production process to produce polyisocyanate and
then the hydrogen chloride produced secondarily is oxidized in the
chlorine production process to produce chlorine to be used in the
carbonyl chloride production process, is repeatedly performed until
an amount of polyisocyanate produced reaches a predetermined
amount. This can realize an effective operation by increasing the
amount of polyisocyanate produced in each process overall and
stepwise until the amount of polyisocyanate produced reaches a
predetermined amount.
[0039] In the polyisocyanate production method of the present
invention, it is preferable that a fixed amount of chlorine of raw
material is used in the carbonyl chloride production process in the
start-up operation as well as in the carbonyl chloride production
process in the load-up operation.
[0040] The present invention provides a polyisocyanate production
method comprising a polyamine production process of producing
polymethylene polyphenylene polyamine by allowing aniline to react
with formaldehyde, using acid catalyst containing hydrochloric
acid, a carbonyl chloride production process of producing carbonyl
chloride by allowing chlorine to react with carbon monoxide, a
polyisocyanate production process of producing polymethylene
polyphenylene polyisocyanate by allowing the carbonyl chloride
produced in the carbonyl chloride production process to react with
the polymethylene polyphenylene polyamine produced in the polyamine
production process, a chlorine production process of producing
chlorine to be used in the carbonyl chloride production process by
oxidizing hydrogen chloride produced secondarily in the
polyisocyanate production process, and a hydrochloric acid
production process of producing hydrochloric acid to be used as the
acid catalyst in the polyamine production process by allowing at
least a part of the hydrogen chloride produced secondarily in the
polyisocyanate production process and/or unoxidized hydrogen
chloride in the chlorine production process to be absorbed or mixed
in water, wherein a start-up operation is first performed by
starting production of polymethylene polyphenylene polyamine in the
polyamine production process, starting production of carbonyl
chloride in the carbonyl chloride production process, starting
production of polymethylene polyphenylene polyisocyanate in the
polyisocyanate production process, starting production of chlorine
in the chlorine production process, and starting production of
hydrochloric acid in the hydrochloric acid production process, and
then a load-up operation, in which any one of the five processes,
i.e., the process of increasing an amount of polymethylene
polyphenylene polyamine produced in the polyamine production
process, the process of increasing an amount of carbonyl chloride
produced in the carbonyl chloride production process, the process
of increasing an amount of polyisocyanate produced in the
polyisocyanate production process, the process of increasing an
amount of chlorine produced in the chlorine production process, and
the process of increasing an amount of hydrochloric acid produced
in the hydrochloric acid production process, is selectively
performed, and then the four other processes are performed is
repeatedly performed until an amount of polymethylene polyphenylene
polyisocyanate produced reaches a predetermined amount.
[0041] According to the polyisocyanate production method of the
present invention, the hydrochloric acid used for producing
polymethylene polyphenylene polyamine can be produced from the
hydrogen chloride produced secondarily in the production of
polymethylene polyphenylene polyisocyanate.
[0042] The present invention provides a polyisocyanate production
method comprising a nitration process of nitrating an aromatic raw
material, using a sulfuric acid and a nitric acid, to introduce a
nitro group in an aromatic ring of the aromatic raw material, a
polyamine production process of producing polyamine by reducing the
nitro group introduced in the aromatic ring of the aromatic raw
material in the nitration process to an amino group, a carbonyl
chloride production process of producing carbonyl chloride by
allowing chlorine to react with carbon monoxide, a polyisocyanate
production process of producing polyisocyanate by allowing the
carbonyl chloride produced in the carbonyl chloride production
process to react with the polyamine produced in the polyamine
production process, a hydrogen chloride oxidation process of
oxidizing hydrogen chloride produced secondarily in the
polyisocyanate production process to produce a mixture of chlorine
and water, and a dehydration process of dehydrating the mixture
produced in the hydrogen chloride oxidation process by putting the
mixture into contact with a sulfuric acid thereby to produce
chlorine, wherein the sulfuric acid used in the dehydration process
is reused in the nitration process.
[0043] According to this method, the sulfuric acid used in the
dehydration process can be reused to nitrate the aromatic raw
material in the nitration process. This can allow effective use of
sulfuric acid and can reduce production costs of
polyisocyanate.
[0044] In the polyisocyanate production method of the present
invention, since in the dehydration process, after the mixture and
the sulfuric acid are supplied to a dehydration column continuously
so that they are continuously contacted with each other in the
dehydration column, the sulfuric acid absorbing the water is
drained continuously, it is preferable that an amount of sulfuric
acid supplied per unit time in the dehydration process is adjusted
to correspond to an amount of sulfuric acid lost per unit time in
the nitration process.
[0045] When an amount of sulfuric acid supplied per unit time in
the dehydration process is adjusted to correspond to an amount of
sulfuric acid lost per unit time in the nitration process, there is
no need to add the sulfuric acid in the nitration process, thus
allowing further effective use of the sulfuric acid.
[0046] In the polyisocyanate production method of the present
invention, it is preferable that in the dehydration process, a
concentration of sulfuric acid supplied to the dehydration column
is not less than 97 weight %.
[0047] When the concentration of sulfuric acid supplied to the
dehydration column is not less than 97 weight %, the dehydration
efficiency can be improved remarkably.
[0048] Further, in the polyisocyanate production method of the
present invention, it is preferable that the chlorine produced in
the dehydration process is allowed to react with carbon monoxide in
the carbonyl chloride production process to produce carbonyl
chloride.
[0049] When the chlorine produced in the dehydration process is
allowed to react with carbon monoxide in the carbonyl chloride
production process to produce carbonyl chloride, the chlorine can
be used without being drained to the outside of the system, which
can allow efficient use of the hydrogen chloride produced
secondarily, while allowing reduction of environmental burdens.
[0050] The present invention provides a polyisocyanate production
system comprising a nitration reactor for nitrating an aromatic raw
material, using a sulfuric acid and a nitric acid, to introduce a
nitro group in an aromatic ring of the aromatic raw material, a
polyamine producing reactor for producing polyamine by reducing the
nitro group introduced in the aromatic ring of the aromatic raw
material in the nitration reactor to an amino group, a carbonyl
chloride producing reactor for producing carbonyl chloride by
allowing chlorine to react with carbon monoxide, a polyisocyanate
producing reactor for producing polyisocyanate by allowing the
carbonyl chloride produced in the carbonyl chloride producing
reactor to react with the polyamine produced in the polyamine
producing reactor, a hydrogen chloride oxidizing reactor for
oxidizing hydrogen chloride produced secondarily in the
polyisocyanate producing reactor to produce a mixture of chlorine
and water, a dehydration column for dehydrating the mixture
produced in the hydrogen chloride oxidizing reactor by putting the
mixture into contact with a sulfuric acid thereby to produce
chlorine, and a sulfuric acid supply line for supplying the
sulfuric acid from the dehydration column to the nitration reactor
so that the sulfuric acid used in the dehydration column can be
reused in the nitration process.
[0051] According to this system, the sulfuric acid used in the
dehydration column is reused to nitrate an aromatic raw material in
the nitration reactor by supplying the sulfuric acid from the
dehydration column to the nitration reactor via the sulfuric acid
supply line. This can allow efficient use of the sulfuric acid,
which can realize reduction of production costs of
polyisocyanate.
[0052] It is preferable that the polyisocyanate production system
of the present invention further comprises a chlorine supply line
for supplying the chlorine produced in the dehydration column from
the dehydration column to the carbonyl chloride producing reactor
so that the chlorine is allowed to react with carbon monoxide in
the carbonyl chloride producing reactor to produce carbonyl
chloride.
[0053] When the chlorine produced in the dehydration column is
supplied from the dehydration column to the carbonyl chloride
producing reactor via the chlorine supply line, the chlorine can be
allowed to react with carbon monoxide in the carbonyl chloride
producing reactor to produce carbonyl chloride. This can allow the
recycle use of chlorine without being drained to the outside of the
system, which can allow efficient use of the hydrogen chloride
produced secondarily, while allowing reduction of environmental
burdens.
EFFECT OF THE INVENTION
[0054] According to the polyisocyanate production method of the
present invention, after chlorine is produced in the chlorine
production process by oxidizing the hydrogen chloride produced
secondarily in the polyisocyanate production process, the chlorine
produced is allowed to react with carbon monoxide in the carbonyl
chloride production process thereby to produce carbonyl chloride.
In short, the chlorine is produced from the hydrogen chloride
produced secondarily and the chlorine thus produced is reused as
the raw material of the carbonyl chloride. This can allow the
recycle use of chlorine without being drained to the outside of the
system, which can allow efficient use of the hydrogen chloride
produced secondarily, while allowing reduction of environmental
burdens.
[0055] According to the polyisocyanate production system of the
present invention, after chlorine is produced in the chlorine
production unit by oxidizing the hydrogen chloride produced
secondarily in the polyisocyanate production unit, the chlorine
produced is supplied to the carbonyl chloride production unit via
the chlorine resupply unit so that the chlorine can be allowed to
react with carbon monoxide in the carbonyl chloride production
process thereby to produce carbonyl chloride. In short, chlorine is
produced from the hydrogen chloride produced secondarily and the
chlorine thus produced is reused as the raw material of the
carbonyl chloride. This can allow the recycle use of chlorine
without being drained to the outside of the system, which can allow
efficient use of the hydrogen chloride produced secondarily, while
allowing reduction of environmental burdens.
BRIEF DESCRIPTION OF THE DRAWINGS
[0056] FIG. 1 is a schematic block diagram showing an embodiment of
a polyisocyanate production system of the present invention.
[0057] FIG. 2 is a flowchart showing an embodiment of the sequence
of a stat-up operation and a load-up operation of the
polyisocyanate production system shown in FIG. 1.
[0058] FIG. 3 is a schematic block diagram showing another
embodiment of the polyisocyanate production system of the present
invention.
[0059] FIG. 4 is a schematic block diagram showing an embodiment of
a dehydration column shown in FIG. 3.
EXPLANATION OF NUMERALS
[0060] 1: Polyisocyanate production system [0061] 2: Carbonyl
chloride producing reactor [0062] 3: Isocyanate producing reactor
[0063] 5: Hydrogen chloride absorbing column [0064] 6: Hydrogen
chloride oxidizing reactor [0065] 8: Chlorine reuse (resupply) line
[0066] 9: Polyamine producing reactor [0067] 10: Hydrochloric acid
reuse (resupply) line [0068] 21: Polyisocyanate production system
[0069] 22: Nitration reactor [0070] 23: Polyamine producing reactor
[0071] 24: Carbonyl chloride producing reactor [0072] 25:
Polyisocyanate producing reactor [0073] 28: Hydrogen chloride
oxidizing reactor [0074] 29: Dehydration column [0075] 31: Sulfuric
acid supply line [0076] 32: Chlorine supply line
EMBODIMENTS OF THE INVENTION
[0077] FIG. 1 is a schematic block diagram showing an embodiment of
a polyisocyanate production system of the present invention. In the
following, an embodiment of the polyisocyanate production method of
the present invention is described with reference to FIG. 1.
[0078] As shown in FIG. 1, a polyisocyanate production system 1
comprises a carbonyl chloride producing reactor 2 for serving as
carbonyl chloride production unit, an isocyanate producing reactor
3 serving as polyisocyanate production unit, a hydrogen chloride
purifying column 4, a hydrogen chloride absorbing column 5 serving
as hydrochloric acid production unit, a hydrogen chloride oxidizing
reactor 6 serving as chlorine production unit, connection lines
(piping) 7 for connection therebetween, and a chlorine resupply
line 8 serving as chlorine resupply unit.
[0079] The carbonyl chloride producing reactor 2 is not limited to
any particular one, as long as it is a reactor for reacting
chlorine (Cl.sub.2) with carbon monoxide (CO) to produce carbonyl
chloride (COCl.sub.2). For example, the carbonyl chloride producing
reactor 2 includes a fixed bed reactor in which activate carbon
catalyst is packed. Further, the carbonyl chloride producing
reactor 2 is connected to an isocyanate producing reactor 3 via a
connection line 7.
[0080] Chlorine gas and carbon monoxide gas, which are raw
materials of carbonyl chloride, are supplied to the carbonyl
chloride producing reactor 2 in such a proportion that carbon
monoxide is supplied more than chlorine by 1-10 mol. When chlorine
is oversupplied, there is a possibility that an aromatic ring and a
hydrogen chloride group of polyisocyanate may be chlorinated in the
isocyanate producing reactor 3 by the oversupplied chlorine.
[0081] An amount of chlorine gas supplied and an amount of carbon
monoxide supplied are properly determined on the basis of an amount
of polyisocyanate produced and an amount of hydrogen chloride gas
produced secondarily.
[0082] In the carbonyl chloride producing reactor 2, chlorine and
carbon monoxide undergo carbonyl chloridation reaction to produce
carbonyl chloride (carbonyl chloride production process). In this
carbonyl chloridation reaction, the carbonyl chloride producing
reactor 2 is set at 0-500.degree. C. and 0-5 MPa gauge, for
example.
[0083] The carbonyl chloride obtained may be put in a liquefied
state by being properly cooled to be liquefied, or may be put in a
solution state by being absorbed in an adequate solvent, in the
carbonyl chloride producing reactor 2 or in separate equipment, not
shown.
[0084] When at least a part of carbonyl chloride is put in the
liquefied state and/or solution state, a concentration of carbon
monoxide contained in the carbonyl chloride can be reduced. This
can reduce a concentration of carbon monoxide gas contained in the
hydrogen chloride gas produced secondarily in isocyanate reaction
mentioned later, thus improving a ratio of conversion of hydrogen
chloride to chlorine in an oxidation reaction of hydrogen chloride
mentioned later. This can improve purity of the chlorine resupplied
from the chlorine reuse line 8 to the carbonyl chloride producing
reactor 2, as mentioned later.
[0085] This means that when a concentration of carbon monoxide
contained in the carbonyl chloride obtained in the carbonyl
chloride production process is reduced, a concentration of carbon
monoxide circulated in the polyisocyanate production system can be
reduced.
[0086] Accordingly, a concentration of carbon monoxide contained in
carbonyl chloride in the liquefied state and/or the solution state
is preferably 1 weight % or less, or more preferably 0.2 weight %
or less.
[0087] When carbonyl chloride is in the liquefied state, a
concentration of carbon monoxide within a system for polyisocyanate
production extending from the polyisocyanate production process to
the chlorine production process can be reduced remarkably. As a
result of this, improvement of basic unit and improvement of
operation performance can be realized in the chlorine production
process.
[0088] Then, the carbonyl chloride thus obtained is supplied to the
isocyanate producing reactor 3 via the connection line 7.
[0089] The isocyanate producing reactor 3 is not limited to any
particular one, as long as it is a reactor for reacting carbonyl
chloride with polyamine to produce polyisocyanate. The isocyanate
producing reactor 3 includes a reactor equipped with a stirring
vane and a reaction column having a perforated plate. Preferably,
the isocyanate producing reactor 3 is configured as a multistage
tank. The isocyanate producing reactor 3 is connected to the
hydrogen chloride purifying column 4 through the connection line
7.
[0090] The carbonyl chloride as a raw material of polyisocyanate
produced in the carbonyl chloride producing reactor 2 is supplied
from the carbonyl chloride producing reactor 2 to the isocyanate
producing reactor 3 via the connection line 7 together with
polyamine as a raw material of polyisocyanate.
[0091] In the isocyanate reaction in the isocyanate producing
reactor 3, a solvent or gas inactive to polyisocyanate may also be
used properly.
[0092] The carbonyl chloride is supplied from the carbonyl chloride
producing reactor 2 in a gaseous state as it is or in the
above-mentioned liquefied or solution state in such a proportion
that carbonyl chloride is supplied more than polyamine by 1-60 mol,
or preferably by 1-10 mol.
[0093] Polyamine used is polyamine corresponding to polyisocyanate
used in the production of polyurethane. No particular limitation is
imposed on polyamine. For example, polyamine is properly selected
from aromatic diamines, such as polymethylene polyphenylene
polyamine (MDA) corresponding to polymethylene polyphenylene
polyisocyanate (MDI) and tolylene diamine (TDA) corresponding to
tolylene diisocyanate (TDI), aralkyl diamines, such as
xylylenediamine (XDA) corresponding to xylylenediisocyanate (XDI)
and tetramethylxylylene diamine (TMXDA) corresponding to
tetramethylxylylene diisocyanate (TMXDI), alicyclic diamines, such
as bis(aminomethyl) norbornane (NBDA) corresponding to
bis(isocyanatomethyl) norbornane (NBDI),
3-aminomethyl-3,5,5-trimethylcyclohexyl amine (IPDA) corresponding
to 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI),
4,4'-methylenebis(cyclohexylamine) (H.sub.12MDA) corresponding to
4,4'-methylenebis(cyclohexylisocyanate) (H.sub.12MDI), and
bis(aminomethyl) cyclohexane (H.sub.6XDA) corresponding to
bis(isocyanatomethyl)cyclohexane (H.sub.6XDI), aliphatic diamines,
such as hexamethylene diamine (HDA) corresponding to hexamethylene
diisocyanate (HDI), and polymethylene polyphenyl polyamine
corresponding to polymethylene polyphenyl polyisocyanate (crude
MDI, polymeric MDI).
[0094] The polyisocyanate production system 1 is suitable for
producing aromatic diisocyanate and polymethylene polyphenyl
polyisocyanate from aromatic diamine and polymethylene polyphenyl
polyamine.
[0095] Though polyamine may be supplied directly, it is preferable
that polyamine is previously dissolved in a solvent to produce e.g.
a 5-30 weight % or preferably 10-25 weight % solution before being
supplied.
[0096] The solvent used is not limited to any particular one. The
solvents that may be used include, for example, aromatic
hydrocarbons, such as toluene and xylene, halogenated hydrocarbons,
such as chlorotoluene, chlorobenzene, and dichlorobenzene, esters,
such as butyl acetate and amyl acetate, and ketones, such as
methylisobutyl ketone and methylethyl ketone. Preferably,
chlorobenzene and dichlorobenzene can be used.
[0097] In the isocyanate producing reactor 3, the carbonyl chloride
and the polyamine undergo isocyanate reaction to produce
polyisocyanate, while also hydrochloric gas (HCl gas) is produced
secondarily (polyisocyanate production process). In the isocyanate
reaction, the above-mentioned solvent is added in the isocyanate
producing reactor 3 separately or together with polyamine and the
isocyanate producing reactor 3 is set at 0-500.degree. C. and 0-5
MPa-gauge, for example.
[0098] The obtained polyisocyanate undergoes aftertreatments, such
as degasification, desolvating, and tar cut, and is then purified,
before it is provided as the raw material of polyurethane.
[0099] The hydrochloric gas produced secondarily is supplied to the
hydrogen chloride purifying column 4 via the connection line 7,
together with the entrained solvent and carbonyl chloride.
[0100] The hydrogen chloride purifying column 4 is not limited to
any particular one, as long as it can purify the hydrochloric gas
produced secondarily by separating the entrained solvent and
carbonyl chloride therefrom. For example, the hydrogen chloride
purifying column 4 includes a tray column and a packed column which
are equipped with a condenser. The hydrogen chloride purifying
column 4 is connected to the hydrogen chloride absorbing column 5
and the hydrogen chloride oxidizing reactor 6 through the
connection line 7.
[0101] In the hydrogen chloride purifying column 4, the carbonyl
chloride is condensed by the condenser or absorbed by the solvent,
whereby the carbonyl chloride is separated from the hydrochloric
gas. Further, a slight amount of solvent in the hydrogen chloride
is separated from the hydrochloric gas by being absorbed in
activated carbon and the like.
[0102] In the hydrogen chloride purifying column 4, a concentration
of an organic material in the hydrochloric gas is reduced to be 1
weight % or less, preferably 0.5 weight % or more preferably 0.1
weight % or less, and a concentration of carbon monoxide in the
hydrochloric gas is reduced to be 10V/V % or less, or preferably
3V/V % or less.
[0103] By reducing impurities in the hydrochloric gas to such a
level, disadvantageous effects on the catalyst, such as decreased
activity or partial deactivation of the catalyst, can be reduced or
prevented in the hydrogen chloride oxidation reaction mentioned
later. This can achieve an improved basic unit and an equalized
temperature distribution of the hydrogen chloride oxidizing reactor
6 and thus stabilization of the hydrogen chloride oxidizing reactor
6. Further, this can improve a ratio of hydrogen chloride to
chlorine.
[0104] Then, a large proportion of the hydrochloric gas purified is
supplied to the hydrogen chloride oxidizing reactor 6 and a part of
the hydrochloric gas purified is supplied to the hydrogen chloride
absorbing column 5. A proportion between the hydrochloric gas
supplied to the hydrogen chloride oxidizing reactor 6 and the
hydrochloric gas supplied to the hydrogen chloride absorbing column
5 is properly determined on the basis of a desired concentration of
the hydrochloric acid in the hydrogen chloride absorbing column 5,
as mentioned later.
[0105] The hydrogen chloride oxidizing reactor 6 is not limited to
any particular one, as long as it is a reactor for oxidizing the
hydrochloric gas to produce chlorine (Cl.sub.2). For example, the
hydrogen chloride oxidizing reactor 6 includes a fluid bed reactor
using chromium oxide as the catalyst and a fixed bed reactor using
ruthenium oxide as the catalyst.
[0106] The hydrogen chloride oxidizing reactor 6 is connected to
the carbonyl chloride producing reactor 2 via a chlorine resupply
line 8 and is connected to the hydrogen chloride absorbing column 5
via the connection line 7.
[0107] When the hydrogen chloride oxidizing reactor 6 comprises the
fluid bed reactor, at least 0.25 mol of oxygen per mol of hydrogen
chloride contained in the hydrochloric gas is supplied to the fluid
bed reactor 6 for the reaction in the presence of chromium oxide at
0.1-5 MPa-gauge and 300-500.degree. C., with reference to Japanese
Unexamined Patent Publication No. 62-275001, for example. An amount
of hydrochloric gas supplied is in the range of e.g. 0.2-1.8
Nm.sup.3/hkg-catalyst.
[0108] When the hydrogen chloride oxidizing reactor 6 comprises the
fixed bed reactor, at least 0.25 mol of oxygen per mol of hydrogen
chloride contained in the hydrochloric gas is supplied to the fixed
bed reactor 6 for the reaction in the presence of
ruthenium-containing catalyst at 0.1-5 MPa and 200-500.degree. C.,
with reference to Japanese Unexamined Patent Publication No.
2000-272906, for example.
[0109] Then, in the hydrogen chloride oxidizing reactor 6, the
hydrochloric gas is oxidized by oxygen (O.sub.2), so that chlorine
is produced and water (H.sub.2O) is produced secondarily (chlorine
production process). In the hydrogen chloride oxidation reaction, a
conversion ratio of hydrogen chloride to chlorine is e.g. 60% or
more, or preferably 70-95%.
[0110] The chlorine obtained is purified on an as-needed basis by a
known process including absorption, dehydration, and separation,
though not shown in particular.
[0111] Then, in the polyisocyanate production system 1, the
chlorine obtained in the hydrogen chloride oxidizing reactor 6 is
supplied to the carbonyl chloride producing reactor 2 via the
chlorine resupply line 8 and is reused as a raw material for
producing the carbonyl chloride in the carbonyl chloride producing
reactor 2.
[0112] As just described, in the polyisocyanate production method
using this polyisocyanate production system 1, after the hydrogen
chloride produced secondarily in the isocyanate producing reactor 3
is oxidized to produce chlorine in the hydrogen chloride oxidizing
reactor 6, the chlorine thus produced is supplied to the carbonyl
chloride producing reactor 2 and is reused as the raw material of
the carbonyl chloride. Thus, this method can allow the recycle use
of chlorine without being drained to the outside of the system of
the polyisocyanate production system 1, which can allow efficient
use of the hydrogen chloride produced secondarily, while allowing
reduction of environmental burdens.
[0113] Unoxidized (unreacted) hydrogen chloride gas and
hydrochloric acid water in the hydrogen chloride oxidizing reactor
6 are supplied therefrom to the hydrogen chloride absorbing column
5 via the connection line 7. The hydrochloric acid water is
produced by making the hydrochloric gas being absorbed in the water
produced secondarily in the hydrogen chloride oxidizing reactor
6.
[0114] The hydrogen chloride absorbing column 5 is not limited to
any particular one, as long as it can adjust a concentration of the
hydrochloric acid water (aqueous solution of hydrogen chloride:
HClaq) by making the hydrogen chloride gas absorbed in water or
hydrochloric acid water. The hydrogen chloride absorbing column 5
includes a known absorbing column.
[0115] Water, the hydrochloric gas and hydrochloric acid water
supplied from hydrogen chloride oxidizing reactor 6 via the
connection line 7, and the hydrochloric gas supplied from the
hydrogen chloride purifying column 4 via the connection line 7 are
supplied to the hydrogen chloride absorbing column 5, in which the
hydrochloric gas is absorbed in the water and the hydrochloric acid
water thereby to produce hydrochloric acid (hydrochloric acid
production process). The hydrochloric acid thus obtained is
provided for industrial purpose as it is or after purified using
activated carbon and the like.
[0116] Since the hydrochloric acid produced in the hydrogen
chloride absorbing column 5 is provided in a desired concentration
for industrial purpose without any need to change, a concentration
of the hydrochloric acid (a concentration of hydrogen chloride
contained in the hydrochloric acid) is adjusted to a desired value
by regulating an amount of water supplied to the hydrogen chloride
absorbing column 5 or by regulating an amount of hydrochloric gas
supplied from the hydrogen chloride purifying column 4 via the
connection line 7. Alternatively, a concentration of the
hydrochloric acid may be adjusted in such a process that after the
hydrochloric acid once absorbed is heated to produce hydrochloric
gas again, the hydrochloric gas thus reproduced is absorbed in a
predetermined amount of water.
[0117] The hydrogen chloride is converted to chlorine at a constant
conversion ratio in the hydrogen chloride oxidizing reactor 6, so
that the remaining hydrogen chloride after conversion to the
chlorine is supplied from the hydrogen chloride oxidizing reactor 6
to the hydrogen chloride absorbing column 5 via the connection line
7 at a fixed ratio. For example, where the conversion ratio in the
hydrogen chloride oxidizing reactor 6 is 80%, 80% hydrogen chloride
is converted to chlorine, while on the other hand, the remaining
20% hydrogen chloride is supplied from in the hydrogen chloride
oxidizing reactor 6 to the hydrogen chloride absorbing column 5 via
the connection line 7.
[0118] Then, a concentration of the hydrochloric acid is adjusted
to a desired value by regulating a volume of water supplied to the
hydrogen chloride absorbing column 5 on the basis of the
hydrochloric gas and the hydrochloric acid water supplied from the
hydrogen chloride oxidizing reactor 6 and the hydrochloric gas
supplied from the hydrogen chloride purifying column 4, or by
regulating a quantity of the hydrochloric gas supplied from the
hydrogen chloride purifying column 4 on the basis of the
hydrochloric gas supplied from the hydrogen chloride oxidizing
reactor 6. This can provide the result that a desired concentration
of the hydrochloric acid can be prepared in the hydrogen chloride
absorbing column 5 without any need to adjust the concentration in
a subsequent process, which can allow the hydrochloric acid to be
directly provided for the industrial purpose.
[0119] In this polyisocyanate production system 1, chlorine (added
chlorine) separately prepared as a raw material is also supplied to
the carbonyl chloride producing reactor 2, in addition to the
chlorine (the recycled chlorine) supplied thereto from the hydrogen
chloride oxidizing reactor 6 via the chlorine resupply line 8.
[0120] An amount of added chlorine supplied is set to correspond to
a required amount of hydrogen chloride for producing the
hydrochloric acid in the hydrogen chloride absorbing column 5 (that
is a shortage of the recycled chlorine). The added chlorine may be
purchased from outside, if required. Alternatively, the
polyisocyanate production system may include added chlorine
production equipment for producing chlorine by a process such as
electrolyzation separate from the polyisocyanate production method
so that the added chlorine may be supplied from such added chlorine
production equipment.
[0121] When the added chlorine is supplied in correspondence with
the required amount of added chlorine for producing the
hydrochloric acid in the hydrogen chloride absorbing column 5, a
mass balance in the polyisocyanate production system 1 can be
stabilized, while the hydrochloric acid of a desired concentration
can be provided from the hydrogen chloride absorbing column 5.
[0122] Then, when tolylene diisocyanate (TDI) in particular is
produced by the polyisocyanate production system 1, carbonyl
chloride is supplied from the carbonyl chloride producing reactor 2
to the isocyanate producing reactor 3 via the connection line 7 and
tolylene diamine (TDA) is also supplied thereto as the
polyamine.
[0123] In the isocyanate producing reactor 3, the TDI is produced
by the reaction between the carbonyl chloride and the TDA.
[0124] When the TDI is produced by this polyisocyanate production
system 1, there can be provided the result that the hydrogen
chloride produced secondarily can be used effectively, while
environmental burdens can be reduced, as mentioned above.
[0125] In the case where the polymethylene polyphenylene
polyisocyanate (MDI) is produced in the polyisocyanate production
system 1 cited above, the polyisocyanate production system 1
includes a polyamine producing reactor 9 serving as polyamine
producing unit for producing polymethylene polyphenylene polyamine
(MDA), as indicated by a dotted line.
[0126] The polyamine producing reactor 9 is not limited to any
particular one, as long as it can allow aniline and formaldehyde to
react with each other using the acid catalyst comprising the
hydrochloric acid thereby to produce the MDA. The polyamine
producing reactor 9 includes, for example, a reactor equipped with
a stirring vane and a reactor having a perforated plate.
Preferably, the polyamine producing reactor 9 is configured as a
multistage tank. The polyamine producing reactor 9 is connected to
the isocyanate producing reactor 3 via the connection line 7 and
also is connected to the hydrogen chloride absorbing column 5 via a
hydrochloric acid resupply line 10 serving as hydrochloric acid
resupply unit.
[0127] The aniline and the formaldehyde, which are raw materials of
polyamine, are supplied to the polyamine producing reactor 9. The
hydrochloric acid is also supplied thereto as the acid catalyst.
This hydrochloric acid is the hydrochloric acid produced in the
hydrogen chloride absorbing column 5 and supplied therefrom to the
reactor 9 via the hydrochloric acid resupply line 10. The hydrogen
acid is supplied thereto separately, as required. In the reaction
between the aniline and the formaldehyde, the inactive solvent and
the inactive gas may be used properly.
[0128] A supply ratio between the aniline and the formaldehyde is
properly selected by a desired multimeric complex ratio of the MDA.
In the polyamine producing reactor 9, the formaldehyde may be
supplied in a multistage manner to the aniline.
[0129] The amount of aniline supplied, the amount of formaldehyde
supplied, and the amount of acid catalyst supplied are properly set
on the basis of an amount of polyisocyanate produced and an amount
of hydrochloric gas produced secondarily.
[0130] In the polyamine producing reactor 9, the aniline and the
formaldehyde react with each other to produce the MDA (polyamine
production process). Then, the MDA thus produced is supplied to the
isocyanate producing reactor 3 via the connection line 7. In the
isocyanate producing reactor 3, the MDI is produced by the
isocyanate reaction between the carbonyl chloride and the MDA.
[0131] When the MDI is produced by this polyisocyanate production
system 1, there can be provided the result that the hydrogen
chloride produced secondarily can be used effectively, while
environmental burdens can be reduced, as mentioned above.
[0132] When the MDI is produced by this polyisocyanate production
system 1, the hydrochloric acid produced in the hydrogen chloride
absorbing column 5 is supplied to the polyamine producing reactor 9
via the hydrochloric acid resupply line 10. Then, the hydrochloric
acid is used as the acid catalyst in the reaction between the
aniline and the formaldehyde in the polyamine producing reactor 9.
This means that the hydrogen chloride produced secondarily in the
isocyanate reaction of the MDI can fill the need for the
hydrochloric acid used as the acid catalyst in the production of
the MDA. This can achieve improvement in production efficiency and
reduction in production cost.
[0133] In the polyisocyanate production system 1 mentioned above,
since Cl atoms circulate in the system and a predetermined amount
of polyisocyanate produced is constantly produced, as described
above, it is required that a start-up operation at the start of
operation and a load-up operation from the start of the operation
until the start of steady operation are performed effectively.
[0134] FIG. 2 is a flowchart showing an embodiment of the sequence
of the stat-up operation and the load-up operation of the
polyisocyanate production system shown in FIG. 1.
[0135] Next, description on the start-up operation and the load-up
operation of this polyisocyanate production system 1 is given with
reference to FIG. 2.
[0136] As shown in FIG. 2, the added chlorine only is used in the
start-up operation (S1-S4) at the starting of the operation. To be
more specific, the added chlorine and carbon monoxide are supplied
to the carbonyl chloride producing reactor 2 (S1), first. The
amount of added chlorine supplied is e.g. 10-50%, or preferably
10-30% where the amount of added chlorine supplied during the
steady operation is 100%.
[0137] Then, in the carbonyl chloride producing reactor 2, carbonyl
chloride is produced by the carbonyl chloridation reaction between
the chlorine and the carbon monoxide (S2).
[0138] Then, the carbonyl chloride produced in the carbonyl
chloride producing reactor 2 is allowed to react with polyamine in
the isocyanate producing reactor 3, whereby polyisocyanate is
produced and hydrochloric gas is produced secondarily (S3).
[0139] Thereafter, the hydrochloric gas produced secondarily is
purified in the hydrogen chloride purifying column 4 and then
oxidized in the hydrogen chloride oxidizing reactor 6 thereby to
produce recycled chlorine (S4).
[0140] Then, in this polyisocyanate production system 1, the
load-up operation (S2-S6) is repeatedly performed during the time
from the start of operation until the start of steady operation. To
be more specific, in addition to the added chlorine, the recycled
chlorine produced in the hydrogen chloride oxidizing reactor 6 is
supplied to the carbonyl chloride producing reactor 2, together
with the carbon monoxide, first (S6).
[0141] The amount of chlorine supplied in this load-up operation
comes to be a total of the added chlorine and the recycled
chlorine. Hence, the amount of chlorine supplied in this load-up
operation is more than the amount of chlorine supplied in the
start-up operation. For example, when 25% of the added chlorine is
supplied in the start-up operation and a conversion ratio of
hydrogen chloride to chlorine is 80%, 20% of the recycled chlorine
is produced in the start-up operation and that 20% of the recycled
chlorine is added to 25% of the added chlorine in the load-up
operation, i.e., 45% of the chlorine is originally supplied in the
load-up operation.
[0142] Then, in the carbonyl chloride producing reactor 2, the
carbonyl chloride is produced by the carbonyl chloridation reaction
between the chlorine and the carbon monoxide (S2). The amount of
carbonyl chloride thus produced increases with the amount of
chlorine supplied.
[0143] Then, the carbonyl chloride produced in the carbonyl
chloride producing reactor 2 is allowed to react with polyamine in
the isocyanate producing reactor 3, whereby polyisocyanate is
produced and hydrochloric gas is produced secondarily (S3). The
amount of polyisocyanate thus produced and the amount of
hydrochloric gas produced secondarily increase with increase in
amount of carbonyl chloride produced.
[0144] Thereafter, the hydrochloric gas produced secondarily is
purified in the hydrogen chloride purifying column 4 and then
oxidized in the hydrogen chloride oxidizing reactor 6 thereby to
produce the recycled chlorine (S4). The amount of recycled chlorine
thus produced increases with an amount of hydrochloric gas produced
secondarily. For example, when 45% of the chlorine is originally
supplied in the load-up operation and a conversion ratio of
hydrogen chloride to chlorine is 80%, 36% of the recycled chlorine
is produced.
[0145] Then, the processes mentioned above (S6-S4) are repeatedly
performed until the amount of polyisocyanate produced reaches its
targeted production amount (i.e. the amount of polyisocyanate
produced in the steady operation), (S5: NO). In these repeated
processes, the amount of carbonyl chloride produced, the amount of
polyisocyanate produced, the amount of hydrochloric gas produced
secondarily, and the amount of recycled chlorine produced increase
with increase in amount of chlorine supplied in each cycle. For
example, when 36% of the recycled chlorine is produced, as
mentioned above, 36% of the recycled chlorine is added to 25% of
the added chlorine, so that an amount of chlorine supplied next
amounts to 61%. With the increase in amount of chlorine supplied,
the amount of carbonyl chloride produced, the amount of
polyisocyanate produced, the amount of hydrochloric gas produced
secondarily, and the amount of recycled chlorine produced
secondarily increase.
[0146] When the amount of polyisocyanate produced increases
gradually and reaches its targeted production amount (i.e. the
amount of polyisocyanate produced in the steady operation), the
load-up operation ends (S5:YES) and then the steady operation
proceeds (S7).
[0147] In the steady operation, an amount of chlorine supplied to
the carbonyl chloride producing reactor 2 (a total amount of added
chlorine and recycled chlorine) is fixed corresponding to the
amount of polyisocyanate produced in the steady operation.
[0148] No particular limitation is imposed on the way of fixing the
amount of chlorine supplied. The amount of chlorine supplied may be
fixed by the following method, for example. Namely, a certain
amount of added chlorine is constantly supplied during the time
from the start of operation until the start of steady operation,
while on the other hand, an amount of hydrochloric gas produced
secondarily in the isocyanate producing reactor 3 to be absorbed
directly in water and hydrochloric acid water in the hydrogen
chloride absorbing column 5 after purified by the hydrogen chloride
purifying column 4 is adjusted (increased) in the steady operation.
This can allow a certain amount of added chlorine to be supplied
constantly, facilitating calculation of the mass balance and the
control of the system.
[0149] The amount of chlorine supplied may be fixed by the
following alternate method, for example. Namely, the amount of
added chlorine may be decreased than that in the load-up operation
so that the amount of chlorine supplied to the carbonyl chloride
producing reactor 2 (a total amount of added chlorine and recycled
chlorine) can be made constant in the steady operation.
[0150] When the start-up operation and the load-up operation are
performed in the steps mentioned above, the effective operation can
be realized by allowing the amount produced in each process to be
increased overall and stepwise until the amount of polyisocyanate
produced reaches an amount of polyisocyanate produced in the steady
operation.
[0151] In the above description, the amount of carbonyl chloride
produced is increased in the carbonyl chloride producing reactor 2
and then the amount of polyisocyanate produced is increased in the
isocyanate producing reactor 3, then the amount of recycled
chlorine produced is increased in the hydrogen chloride oxidizing
reactor 6, the sequence of the process of the load-up operation can
be selectively determined in the polyisocyanate production system
1.
[0152] The load-up operation may be performed in the following
sequences, for example. After the amount of polyisocyanate produced
is increased in the isocyanate producing reactor 3 by adjusting the
amount of polyamine supplied in the isocyanate producing reactor 3,
the amount of recycled chlorine is increased in the hydrogen
chloride oxidizing reactor 6 and then the amount of carbonyl
chloride produced is increased in the carbonyl chloride producing
reactor 2.
[0153] Further, the load-up operation may alternatively be
performed in the following sequences, for example. After the amount
of hydrochloric gas produced secondarily in the isocyanate
producing reactor 3 to be absorbed directly in water and
hydrochloric acid water in the hydrogen chloride absorbing column 5
after purified in the hydrogen chloride purifying column 4 is
adjusted (increased) to increase the amount of recycled chlorine
produced in the hydrogen chloride oxidizing reactor 6, the amount
of carbonyl chloride produced is increased in the carbonyl chloride
producing reactor 2 and then the amount of polyisocyanate produced
is increased in the isocyanate producing reactor 3.
[0154] It is preferable that in the start-up operation, the
warming-up operation is performed before the recycled chlorine is
produced in the hydrogen chloride oxidizing reactor 6.
[0155] In the case where the hydrogen chloride oxidizing reactor 6
comprises the fluid bed reactor, the fluid bed reactor is
previously put in an circulation operation to be set at a
predetermined temperature and pressure, using e.g. an inactive gas,
such as nitrogen, or air, chlorine, or an inactive gas containing
chlorine, or hydrogen chloride, before the hydrochloric gas is
supplied to the hydrogen chloride oxidizing reactor 6.
[0156] When the fluid bed reactor is thus previously put in a
circulation operation, the start-up operation can be performed
further effectively.
[0157] FIG. 3 is a schematic block diagram showing another
embodiment of the polyisocyanate production system of the present
invention. In the following, another embodiment of the
polyisocyanate production system of the present invention is
described with reference to FIG. 3.
[0158] As shown in FIG. 3, a polyisocyanate production system 21
comprises a nitration reactor 22, a polyamine producing reactor 23,
a carbonyl chloride producing reactor 24, a polyisocyanate
producing reactor 25, a hydrogen chloride purifying column 26, a
hydrogen chloride absorbing column 27, a hydrogen chloride
oxidizing reactor 28, a dehydration column 29, a connection line
(piping) 30 for connecting them, a sulfuric acid supply line 31,
and a hydrochloric acid supply line 32.
[0159] The nitration reactor 22 is not limited to any particular
one, as long as it is a reactor for performing nitration of
aromatic raw material using sulfuric acid and nitric acid. The
nitration reactor 22 includes, for example, a reactor equipped with
a stirring vane and a reactor having a perforated plate.
Preferably, the nitration reactor 22 is configured as a multistage
tank. Further, the nitration reactor 22 is connected to the
polyamine producing reactor 23 via the connection line 30.
[0160] The aromatic raw material and the nitric acid are
continuously supplied to the nitration reactor 22 and the sulfuric
acid used in circulation in the nitration process. Further, an
amount of sulfuric acid corresponding to an amount of sulfuric acid
lost per unit time in the nitration process is continuously
supplied from the dehydration column 29 to the nitration reactor
22.
[0161] The aromatic raw material which includes benzenes and
derivatives thereof is selected from e.g. benzene, toluene, etc.
corresponding to polyisocyanate produced. Specifically, when
polymethylene polyphenylene polyisocyanate (MDI) is produced,
benzene is used and mononitrated in the nitration reactor 22. On
the other hand, when tolylene diisocyanate (TDI) is produced,
toluene is used and dinitrated in the nitration reactor 22.
[0162] For example, 50-100 weight % nitric acid (aqueous solution)
is used as the nitric acid. In the mononitration, the nitric acid
is continuously supplied in the proportion of e.g. 0.7-1.5 mol, or
preferably 0.8-1.2 mol, per mol of aromatic raw material. On the
other hand, in the dinitration, the nitric acid is continuously
supplied in the proportion of e.g. 1.5-2.5 mol, or preferably
1.6-2.2 mol, per mol of aromatic raw material.
[0163] The sulfuric acid supplemented corresponding to the amount
lost in the nitration process is, for example, 60-100 weight %, or
preferably 70-98 weight %, sulfuric acid (aqueous solution). It is
supplied continuously from the dehydration column 29 via the
sulfuric acid supply line 31, as mentioned later.
[0164] In the nitration reactor 22, the aromatic raw material
contacts with sulfuric acid and nitric acid (mixed acid) and is
nitrated (more specifically, mononitrated when benzene is used, and
dinitrated when toluene is used), so that one or two nitro groups
is/are introduced in an aromatic ring of the aromatic raw material
(in the nitration process). In this nitration process, the
nitration reactor 22 is set at e.g. 0-200.degree. C., or preferably
30-180.degree. C.
[0165] As a result of this, a nitrated aromatic compound having one
or two nitro groups introduced in the aromatic ring is produced in
the nitration reactor 22. More concretely, when benzene is used as
the aromatic raw material, nitrobenzene is produced as the nitrated
aromatic compound. On the other hand, when toluene is used as the
aromatic raw material, dinitrotoluene is produced as the nitrated
aromatic compound.
[0166] In this process, a nitric acid contained in the mixed acid
is consumed in the nitration reaction and also water is produced.
The mixed acid used for the reaction is diluted with product water
and introduced water from the aqueous nitric acid solution used,
resulting in waste acid consisting primarily of sulfuric acid that
may contain the remaining nitric acid depending on the
circumstances.
[0167] Since the nitrated aromatic compound produced is dispersed
in the waste acid, the nitrated aromatic compound and the waste
acid undergo the liquid-liquid separation to separate the waste
acid from the nitrated aromatic compound. The waste acid separated
is circulated and reused for the nitration. In this separation
process, the waste acid that cannot be separated from the nitrated
aromatic compound comes to be a loss.
[0168] When the waste acid is recycled, water corresponding to the
product water in nitration and to the introduced water is condensed
within the system or outside the system and is removed therefrom,
so that it has a concentration of the order of e.g. 60-95 weight %
for the reuse. A loss is generated in this condensation as
well.
[0169] In the case of the sulfuric acid, the total loss amounts to
e.g. 0.01-1 weight %/h with respect to the total amount of sulfuric
acid.
[0170] The polyamine producing reactor 23 is not limited to any
particular one, as long as it is a reactor for performing reduction
of a nitro group of the nitrated aromatic compound to an amino
group. The polyamine producing reactor 23 is properly selected from
a reactor equipped with a stirring vane, a fluid bed reactor, a
fixed bed reactor, etc. Preferably, the polyamine producing reactor
23 is configured as a multistage tank. Further, the polyamine
producing reactor 23 is connected to the polyisocyanate producing
reactor 25 via the connection line 30.
[0171] Hydrogenerated catalyst (reduction catalyst) is charged in
the polyamine producing reactor 23, to reduce the nitro group of
the nitrated aromatic compound to the amino group, and the hydrogen
gas (H.sub.2) is continuously supplied to the polyamine producing
reactor 23.
[0172] The hydrogenerated catalyst is not limited to any particular
one. It can be selected from known catalysts containing metal, such
as Ni, Mo, Fe, Co, Cu, Pt, Pd, and Rh. Industrially, palladium
carbon catalyst or Raney nickel catalyst is preferably used. An
amount of the hydrogenerated catalyst used is e.g. 0.001-1 parts by
weight, or preferably 0.01-0.1 parts by weight, per 100 parts by
weight of the nitrated aromatic compound supplied, though it is not
particularly limited thereto.
[0173] The nitrated aromatic compound is continuously supplied from
the nitration reactor 22 to the polyamine producing reactor 23 via
the connection line 30. Then, the nitro group of the nitrated
aromatic compound is reduced to the amino group (polyamine
production process). In this polyamine production process, the
polyamine producing reactor 23 is set at e.g. 0-10 MPa-gauge, or
preferably 0.1-7 MPa-gauge, at e.g. 20-250.degree. C., or
preferably 50-200.degree. C.
[0174] Thus, the nitro group of the nitrated aromatic compound is
reduced to the amino group in the polyamine producing reactor 23.
To be more specific, when the nitrated aromatic compound is
dinitrotoluene, toluene diamine (TDA) is produced as the
polyamine.
[0175] On the other hand, when the nitrated aromatic compound is
nitrobenzene, aniline is produced. When the nitrated aromatic
compound is nitrobenzene, in other words, when benzene is used as
the aromatic raw material, the polyamine producing reactor 23 is
provided with a condensation tank, arranged at a location
downstream of the reactor, for condensing aniline and formaldehyde
to produce polymethylene polyphenyl polyamine.
[0176] A known reactor is used as the condensation tank. The
condensation tank is preferably configured as the multistage tank.
The aniline produced, formaldehyde and the hydrochloric acid are
continuously supplied to the condensation tank to produce
polymethylene polyphenyl polyamine (MDA).
[0177] The formaldehyde is supplied continuously in the proportion
of e.g. 0.3-0.6 mol, or preferably 0.4-0.5 mol, per mol of
aniline.
[0178] The hydrochloric acid is supplied continuously in the
proportion of e.g. 0.2-1 mol, or preferably 0.3-0.7 mol, per mol of
aniline.
[0179] Then, the aniline is continuously supplied to the
condensation tank. As a result of this, the aniline and the
formaldehyde are condensed in the presence of hydrochloric acid to
produce polymethylene polyphenyl polyamine (MDA) as the
polyamine.
[0180] Pursuant to Japanese Unexamined Patent Publication No.
3-294249, the aniline and the formaldehyde can be condensed in the
presence of hydrochloric acid to produce polymethylene polyphenyl
polyamine (MDA) as the polyamine.
[0181] The carbonyl chloride producing reactor 24 is not limited to
any particular one, as long as it is a reactor for allowing the
chlorine (Cl.sub.2) to react with monoxide (CO) to produce carbonyl
chloride (COCl.sub.2). For example, the carbonyl chloride producing
reactor 24 comprises the fixed bed reactor packed with activated
carbon catalyst, and the like. Further, the carbonyl chloride
producing reactor 24 is connected to the polyisocyanate producing
reactor 25 via the connection line 30.
[0182] Chlorine gas and carbon monoxide gas, serving as raw
materials, are supplied to the carbonyl chloride producing reactor
24 in such a proportion that the carbon monoxide is supplied more
than the chlorine by 1-10 mol %. When chlorine is oversupplied,
there is a possibility that an aromatic ring and a hydrocarbon
group of polyisocyanate may be chlorinated in the polyisocyanate
producing reactor 25 by the oversupplied chlorine.
[0183] An amount of chlorine gas supplied and an amount of carbon
monoxide gas supplied are properly determined on the basis of an
amount of polyisocyanate produced and an amount of hydrogen
chloride gas produced secondarily. The chlorine gas supplied from a
dehydration column 29 via the chlorine supply line 32 is used as
the chlorine gas, as mentioned later.
[0184] Then, in the carbonyl chloride producing reactor 24, the
chlorine and the carbon monoxide react with each other to produce
carbonyl chloride (carbonyl chloride production process). In this
reaction, the carbonyl chloride producing reactor 24 is set at
0-500.degree. C. and 0-5 MPa-gauge, for example.
[0185] The carbonyl chloride obtained may be put in a liquefied
state by being properly cooled to be liquefied in the carbonyl
chloride producing reactor 24 or may be put in a solution state by
being absorbed in an adequate solvent. If necessary, the carbon
monoxide contained in the carbonyl chloride obtained may be removed
and then the resulting carbonyl chloride can be resupplied to the
carbonyl chloride producing reactor 24.
[0186] When at least a part of carbonyl chloride is put in the
liquefied state and/or solution state, a concentration of carbon
monoxide contained in the carbonyl chloride can be reduced. This
can improve a ratio of conversion of hydrogen chloride to chlorine
in hydrogen chloride oxidation reaction mentioned later. The
carbonyl chloride can be put in the liquefied state, for example,
using a condenser provided at a location downstream of the fixed
bed reactor to liquefy the carbonyl chloride in the carbonyl
chloride producing reactor 24. In this liquefaction process, a
concentration of carbon monoxide contained in the carbonyl chloride
is preferably set at 1 weight % or less.
[0187] The polyisocyanate producing reactor 25 is not limited to
any particular one, as long as it is a reactor for performing the
reaction of carbonyl chloride with polyamine to produce
polyisocyanate. The polyisocyanate producing reactor 25 includes,
for example, a reactor equipped with a stirring vane and a reactor
having a perforated plate. Preferably, the polyisocyanate producing
reactor 25 is configured as a multistage tank. The polyisocyanate
producing reactor 25 is connected to the hydrogen chloride
purifying column 26 through the connection line 30.
[0188] The carbonyl chloride produced in the carbonyl chloride
producing reactor 24 is supplied to the polyisocyanate producing
reactor 25 from the carbonyl chloride producing reactor 24 via the
connection line 7. In addition, the polyamine produced in the
polyamine producing reactor 23 is also supplied to the
polyisocyanate producing reactor 25 from the polyamine producing
reactor 23 via the connection line 30.
[0189] The carbonyl chloride is supplied from the carbonyl chloride
producing reactor 24 in a gaseous state as it is or in the
above-mentioned liquefied or solution state in such a proportion
that carbonyl chloride is supplied more than polyamine by 1-60
mol.
[0190] Though the polyamine may be supplied directly, it is
preferable that the polyamine is previously dissolved in a solvent
to produce a 5-30 weight % solution before being supplied.
[0191] The solvent used is not limited to any particular one. The
solvents that may be used include, for example, aromatic
hydrocarbons, such as toluene and xylene, halogenated hydrocarbons,
such as chlorotoluene, chlorobenzene, and dichlorobenzene, esters,
such as butyl acetate and amyl acetate, and ketones, such as
methylisobutyl ketone and methyl ethyl ketone. Preferably,
chlorobenzene and dichlorobenzene can be used.
[0192] In the polyisocyanate producing reactor 25, the carbonyl
chloride and the polyamine react with each other to produce
polyisocyanate, while also hydrochloric gas (HCl gas) is produced
secondarily (polyisocyanate production process). In this reaction,
the above-mentioned solvent is added in the polyisocyanate
producing reactor 25 separately or together with the polyamine. The
polyisocyanate producing reactor 25 is set at 0-250.degree. C. and
0-5 MPa-gauge, for example.
[0193] The polyisocyanate produced undergoes aftertreatments, such
as degasification, desolvating, and tar cut, and then purified,
before it is provided as the raw material of polyurethane.
[0194] For example, when the polyamine is toluene diamine (TDA),
tolylene diisocyanate (TDI) is provided as the polyisocyanate. When
the polyamine is polymethylene polyphenyl polyamine (MDA),
polymethylene polyphenyl polyisocyanate (MDI) is provided as the
polyisocyanate.
[0195] The hydrochloric gas produced secondarily is supplied to the
hydrogen chloride purifying column 26 via the connection line 30,
together with the entrained solvent and carbonyl chloride.
[0196] The hydrogen chloride purifying column 26 is not limited to
any particular one, as long as it can purify the hydrochloric gas
by separating the entrained solvent and carbonyl chloride
therefrom. For example, the hydrogen chloride purifying column 26
includes a tray column and a packed column, which are equipped with
a condenser. The hydrogen chloride purifying column 26 is connected
to the hydrogen chloride oxidizing reactor 28 via the connection
line 30.
[0197] In the hydrogen chloride purifying column 26, the carbonyl
chloride is condensed by the condenser or absorbed by the solvent,
whereby the carbonyl chloride is separated from the hydrochloric
gas. Further, a slight amount of solvent in the hydrogen chloride
is separated from the hydrochloric gas by being absorbed in
activated carbon and the like.
[0198] In the hydrogen chloride purifying column 26, a
concentration of an organic material in the hydrochloric gas is
preferably reduced to be 1 weight % or less, or preferably 0.1
weight % or less, and a concentration of carbon monoxide in the
hydrochloric gas is preferably reduced to be 10 volume % or less,
or preferably 3 volume % or less. By reducing impurities in the
hydrochloric gas to such a level, disadvantageous effects on the
catalyst, such as decreased activity or partial deactivation of the
catalyst, can be reduced or prevented in the hydrogen chloride
oxidation reaction mentioned later. This can realize improvement in
basic unit, equalization in temperature distribution in hydrogen
chloride oxidation reaction, and equalization in temperature
distribution of the reactor and thus stabilization of the reactor.
Further, this can improve a conversion ratio of hydrochloric gas to
chlorine.
[0199] Then, the hydrochloric gas purified is supplied to the
hydrogen chloride oxidizing reactor 28.
[0200] The hydrogen chloride oxidizing reactor 28 is not limited to
any particular one, as long as it is a reactor for performing
oxidation of the hydrochloric gas to produce chlorine (Cl.sub.2).
For example, the hydrogen chloride oxidizing reactor 28 includes a
fluid bed reactor using chromium oxide as the catalyst and a fixed
bed reactor using ruthenium oxide as the catalyst. The hydrogen
chloride oxidizing reactor 28 is connected to the hydrogen chloride
absorbing column 27 via the connection line 30.
[0201] When the hydrogen chloride oxidizing reactor 28 comprises
the fluid bed reactor, at least 0.25 mol of oxygen per mol of
hydrogen chloride contained in the hydrochloric gas is supplied for
the reaction in the presence of chromium oxide at 0.1-5 MPa-gauge
and 300-500.degree. C., with reference to Japanese Unexamined
Patent Publication No. 62-275001, for example. An amount of
hydrochloric gas supplied is in the range of e.g. 0.2-1.8
Nm.sup.3/h-kg-catalyst.
[0202] When the hydrogen chloride oxidizing reactor 28 comprises
the fixed bed reactor, at least 0.25 mol of oxygen per mol of
hydrogen chloride contained in the hydrochloric gas is supplied for
the reaction in the presence of ruthenium-containing catalyst at
0.1-5 MPa, and 200-500.degree. C., with reference to Japanese
Unexamined Patent Publication No. 2000-272906, for example.
[0203] Then, in the hydrogen chloride oxidizing reactor 28, the
hydrochloric gas is oxidized by oxygen (O.sub.2), so that chlorine
is produced and water (H.sub.2O) is produced secondarily (hydrogen
chloride oxidation process). In this oxidation reaction (hydrogen
chloride oxidation reaction), a conversion ratio of hydrogen
chloride to chlorine is e.g. 60% or more, or preferably 70-95%.
[0204] The mixture of chlorine, water produced secondarily, and
unoxidized (unreacted) hydrogen chloride gas (including
hydrochloric acid water produced by water absorption) produced in
the hydrogen chloride oxidizing reactor 28 is supplied to the
hydrogen chloride absorbing column 27 via the connection line
30.
[0205] The hydrogen chloride absorbing column 27 is not limited to
any particular one, as long as it can adjust a concentration of the
hydrochloric acid water (aqueous solution of hydrogen chloride:
HClaq) by making the unoxidized (unreacted) hydrogen chloride gas
(including hydrochloric acid water produced by water absorption)
absorbed in water or hydrochloric acid water. The hydrogen chloride
absorbing column 27 includes a known absorbing column. The hydrogen
chloride absorbing column 27 is connected to the dehydration column
29 via the connection line 30.
[0206] In the hydrogen chloride absorbing column 27, the hydrogen
chloride gas contained in the mixture supplied thereto from the
hydrogen chloride oxidizing reactor 28 via the connection line 30
is absorbed in water and hydrochloric acid water thereby to produce
hydrochloric acid (hydrochloric acid production process). The
hydrochloric acid thus produced is provided for industrial purpose
as it is or after purified properly.
[0207] Since the hydrochloric acid produced in the hydrogen
chloride absorbing column 27 is provided as it is in a desired
concentration for industrial purpose, a concentration of the
hydrochloric acid (a concentration of hydrogen chloride contained
in the hydrochloric acid) is adjusted to a desired value by
regulating an amount of water supplied to the hydrogen chloride
absorbing column 27. Alternatively, the concentration of the
hydrochloric acid may be adjusted in such a process in which after
the hydrochloric acid once absorbed is heated to produce
hydrochloric gas again, the hydrochloric gas thus reproduced is
absorbed in a predetermined amount of water.
[0208] Then, in the hydrogen chloride absorbing column 27, the
hydrochloric gas contained in the mixture supplied from the
hydrogen chloride oxidizing reactor 28 via the connection line 30
is removed as hydrochloric acid by being absorbed in water, thereby
to produce a mixed gas comprising primarily chlorine not absorbed
in water. This mixed gas is the mixture of chlorine and water
corresponding to vapor pressure. This mixed gas is supplied to the
dehydration column 29 via the connection line 30.
[0209] The dehydration column 29 is not limited to any particular
one, as long as it can allow the mixed gas of chlorine and water to
contact with sulfuric acid (H.sub.2SO.sub.4) to remove water from
the mixed gas. The dehydration column 29 includes a known
dehydration column. The dehydration column 29 is connected to the
nitration reactor 22 via the sulfuric acid supply line 31 and also
connected to the carbonyl chloride producing reactor 24 via the
chlorine supply line 32.
[0210] For example, a dehydration column 40 shown in FIG. 4 is used
as the dehydration column 29.
[0211] As shown in FIG. 4, the dehydration column 40 is in a sealed
cylindrical form extending vertically and is provided with filling
chambers 41 at upper, middle and lower portions thereof. These
filling chambers 41 are spaced apart from each other and are packed
with filler such as Raschig ring, Berl saddle, and the like.
[0212] The dehydration column 40 connects at its lower portion with
the connection line 30 connected to the hydrogen chloride absorbing
column 27 and connects at its upper portion with a sulfuric acid
falling line 42 for allowing the falling of the sulfuric acid.
Further, it connects at its bottom with the sulfuric acid supply
line 31 and connects at its top with the chlorine supply line
32.
[0213] Further, the dehydration column 40 connects with a lower
circulation line 43 for connecting its portion between the lower
filling chamber 41 and the middle filling chamber 41 to the
sulfuric acid supply line 31. A cooler 44 is interposed in the
lower circulation line 43. The dehydration column 40 also connects
with an upper circulating line 45 for connecting its portion
between the lower filling chamber 41 and the middle filling chamber
41 to its portion between the middle filling chamber 41 and the
upper filling chamber 41. A cooler 44 is interposed in the upper
circulation line 45.
[0214] The mixed gas of chlorine and water is continuously supplied
to the dehydration column 40 from the lower connection line 30,
while also at least 97 weight % of sulfuric acid (aqueous
solution), or preferably 98 weight % of sulfuric acid (aqueous
solution) is continuously supplied thereto from the upper sulfuric
acid falling line 42.
[0215] This allows falling of the sulfuric acid, thus allowing the
sulfuric acid to contact with the mixed gas continuously in the
countercurrent manner and allowing the effective gas-liquid contact
in the respective filling chambers 41 in particular, to absorb the
water contained in the mixed gas for dehydration (dehydration
process). The hydrochloric gas obtained from the dehydration of the
mixed gas is drained to the chlorine supply line 32
continuously.
[0216] On the other hand, the sulfuric acid absorbing water becomes
e.g. 70-80 weight % (aqueous solution) sulfuric acid and thereafter
is drained to the sulfuric acid supply line 31 continuously.
[0217] When the sulfuric acid absorbs water, heat is generated in
the dehydration column 40. However, the aqueous sulfuric acid
solution is partly circulated in the dehydration column 40 via the
lower circulation line 43 and the upper circulation line 45, and
the internal temperature of the dehydration column 40 is controlled
to e.g. 0-60.degree. C., or preferably 10-40.degree. C., by the
coolers 44 interposed in the lower circulation line 43 and the
upper circulation line 45, respectively.
[0218] Then, the sulfuric acid drained from the dehydration column
29 to the sulfuric acid supply line 31 and absorbing water is
supplied to the nitration reactor 22 via the sulfuric acid supply
line 31 and is used as the sulfuric acid for the nitration. An
amount of sulfuric acid supplied from the sulfuric acid supply line
31 to the nitration reactor 22 (an amount supplied per means of
time) corresponds to an amount of sulfuric acid lost in the
nitration reactor 22. The amount of sulfuric acid thus supplied is
adjusted by adjusting an amount of sulfuric acid supplied from the
sulfuric acid falling line 42 in the dehydration column 40.
[0219] The sulfuric acid drained from the dehydration column 29 to
the sulfuric supply line 31 and absorbing water may be condensed so
that it can have a concentration of the order of e.g. 88-95 weight
% before it is supplied to the nitration reactor 22 via the
sulfuric supply line 31. In this case, the sulfuric acid and water
are entrained to generate a loss of sulfuric acid. In the
adjustment process described above, the loss including the amount
of loss resulting from the condensation of the sulfuric acid is
also adjusted.
[0220] Further, the chlorine drained from the dehydration column 29
to the chlorine supply line 32 and dried by the dehydration is
supplied to the carbonyl chloride producing reactor 24 via the
chlorine supply line 32 and is used as the raw material for
producing the carbonyl chloride.
[0221] In addition to the chlorine (the recycled chlorine) supplied
from the chlorine supply line 32, chlorine (added chlorine)
separately prepared as raw material is also supplied to the
carbonyl chloride producing reactor 24. An amount of added chlorine
supplied is set to correspond to a required amount of hydrogen
chloride (or a shortage of the recycled chlorine) for producing the
hydrochloric acid in the hydrogen chloride absorbing column 27. The
added chlorine may be purchased from outside, if required.
Alternatively, the polyisocyanate production system 21 may include
added chlorine production equipment for producing chlorine by a
process such as electrolyzation separate from the polyisocyanate
production method so that the added chlorine may be supplied from
such added chlorine production equipment.
[0222] When the added chlorine is supplied corresponding to the
required amount of added chlorine for producing the hydrochloric
acid in the hydrogen chloride absorbing column 27, a mass balance
of the polyisocyanate production system 21 can be stabilized, while
the hydrochloric acid of a desired concentration can be achieved
from the hydrogen chloride absorbing column 27.
[0223] In this polyisocyanate production system 21, since the
sulfuric acid used for the dehydration in the dehydration column 29
can be used for the nitration of the aromatic raw material in the
nitration reactor 22, the effective usage of the sulfuric acid used
for the dehydration can be achieved and reduction of the production
cost of polyisocyanate can be achieved.
[0224] That is, in this polyisocyanate production system 21, when
the mixed gas of chlorine and water is dehydrated in the
dehydration column 29, using at least 97 weight % concentrated
sulfuric acid, the dehydration efficiency can be improved
remarkably.
[0225] On the other hand, the sulfuric acid, after dehydrated,
absorbs water, so that its concentration reduces to 70-80 W/W %.
When the sulfuric acid is tried to be condensed so that it can have
a concentration of 97 W/W % or more for the circulation use, the
number of processes required for the concentration is increased
significantly, causing cost rise. On the other hand, when the
sulfuric acid after dehydration is disposed without being recycled,
the consumption of the sulfuric acid increases significantly, then
still causing inevitable cost rise.
[0226] However, in this polyisocyanate production system 21, since
the sulfuric acid used for the dehydration in the dehydration
column 29 is reused for the nitration of the aromatic raw material
in the nitration reactor 22, the sulfuric acid used for the
dehydration can be utilized effectively without any need to be
condensed to a high concentration, thus achieving reduced
production cost of polyisocyanate.
[0227] Further, in this polyisocyanate production system 21, since
the amount per means of time of sulfuric acid supplied from the
sulfuric acid falling line 42 is adjusted in the dehydration column
29 to correspond to an amount of sulfuric acid lost in the
nitration reactor 22, there is no need to add the sulfuric acid to
the nitration reactor 22, thus allowing further effective use of
the sulfuric acid.
[0228] Further, in this polyisocyanate production system 21, the
chlorine dried in the dehydration column 29 by the dehydration is
purified by a known method on an as-needed basis so that it is
reused as the raw material for producing the carbonyl chloride in
the carbonyl chloride producing reactor 24, the chlorine can be
recycled without being drained to the outside of the system. Hence,
the hydrochloric gas produced secondarily can be used effectively,
while achieving reduction of environmental burdens.
INDUSTRIAL APPLICABILITY
[0229] The present invention is effectively applicable to a
polyisocyanate production method for producing polyisocyanate used
as a raw material of polyurethane and is also effectively
applicable to a polyisocyanate production system for performing the
polyisocyanate production method.
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