U.S. patent application number 09/790053 was filed with the patent office on 2001-07-05 for production process for (poly)alkylene glycol monoalkyl ether.
This patent application is currently assigned to Nippon Shokubai Co., Ltd.. Invention is credited to Kadono, Yukio, Kirishiki, Masaru, Onda, Yoshiyuki, Tsuneki, Hideaki.
Application Number | 20010007047 09/790053 |
Document ID | / |
Family ID | 26577312 |
Filed Date | 2001-07-05 |
United States Patent
Application |
20010007047 |
Kind Code |
A1 |
Onda, Yoshiyuki ; et
al. |
July 5, 2001 |
Production process for (poly)alkylene glycol monoalkyl ether
Abstract
The present invention provides a process for producing a
(poly)alkylene glycol monoalkyl ether with high selectivity and
high yield. In this process, the (poly)alkylene glycol monoalkyl
ether is produced by reacting an olefin and a (poly)alkylene glycol
in the presence of a catalyst, wherein: 1) a crystalline
metallosilicate is used as the catalyst, and at least a portion of
the used catalyst is regenerated, and the regenerated catalyst is
recycled as the catalyst for the reaction; or 2) the reaction
between the olefin and the (poly)alkylene glycol is carried out in
the presence of either or both of a (poly)alkylene glycol dialkyl
ether and an alcohol.
Inventors: |
Onda, Yoshiyuki; (Suita-shi,
JP) ; Kirishiki, Masaru; (Suita-shi, JP) ;
Tsuneki, Hideaki; (Shinagawa-ku, JP) ; Kadono,
Yukio; (Yokohama-shi, JP) |
Correspondence
Address: |
ROBERT J JACOBSON PA
650 BRIMHALL STREET SOUTH
ST PAUL
MN
551161511
|
Assignee: |
Nippon Shokubai Co., Ltd.
|
Family ID: |
26577312 |
Appl. No.: |
09/790053 |
Filed: |
February 21, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09790053 |
Feb 21, 2001 |
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09410893 |
Oct 3, 1999 |
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09410893 |
Oct 3, 1999 |
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08980577 |
Dec 1, 1997 |
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5994595 |
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Current U.S.
Class: |
568/697 ;
568/606; 568/613; 568/618; 568/619 |
Current CPC
Class: |
C07C 41/42 20130101;
C07C 41/06 20130101; Y02P 20/584 20151101; C07C 41/42 20130101;
C07C 43/13 20130101; C07C 41/06 20130101; C07C 43/11 20130101; C07C
43/13 20130101; C07C 41/06 20130101 |
Class at
Publication: |
568/697 ;
568/606; 568/613; 568/618; 568/619 |
International
Class: |
C07C 043/11; C07C
043/18; C07C 043/20; C07C 041/00; C07C 043/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 6, 1996 |
JP |
8-342617 |
Dec 6, 1996 |
JP |
8-342618 |
Claims
What is claimed is:
1. A process for producing a (poly)alkylene glycol monoalkyl ether,
comprising the step of reacting a (poly)alkylene glycol and an
olefin in the presence of a catalyst, thus obtaining the
(poly)alkylene glycol monoalkyl ether, with the process being
characterized in that a crystalline metallosilicate is used as the
catalyst, and further characterized by further comprising the steps
of: regenerating at least a portion of the used catalyst; and
recycling the regenerated portion of the used catalyst as the
catalyst for the reaction between the (poly)alkylene glycol and the
olefin.
2. A process according to claim 1, wherein the regeneration of the
catalyst is carried out by thermal treatment of the catalyst at
450.degree.C. or higher under an oxygen-containing gas
atmosphere.
3. A process according to claim 1, wherein the crystalline
metallosilicate is a BEA type metallosilicate.
4. A process according to claim 1, further comprising the steps of:
extracting at least a portion of a slurry containing the catalyst
and an unreacted residue of the (poly)alkylene glycol; and
recovering the catalyst from the slurry to regenerate the
catalyst.
5. A process according to claim 4, further comprising the step of
recovering the (poly)alkylene glycol from the slurry by
distillation under temperature conditions of 180.degree.C. or
lower, when the catalyst is also recovered from the slurry.
6. A process according to claim 4, further comprising the step of
recovering the (poly)alkylene glycol from the slurry by
distillation within 30 minutes, when the catalyst is also recovered
from the slurry.
7. A process according to claim 1, wherein: the (poly)alkylene
glycol monoalkyl ether is a (poly)alkylene glycol mono-higher-alkyl
ether; and the olefin is a long chain olefin.
8. A process according to claim 1, wherein the regeneration of at
least a portion of the used catalyst is carried out after the
catalyst is used for 0.02 to 100 hours for the reaction.
9. A process for producing a (poly)alkylene glycol monoalkyl ether,
comprising the step of reacting an olefin and a (poly)alkylene
glycol in the presence of a catalyst, thus obtaining the
(poly)alkylene glycol monoalkyl ether, with the process being
characterized in that the reaction between the olefin and the
(poly)alkylene glycol is carried out in the presence of either or
both of a (poly)alkylene glycol dialkyl ether and an alcohol.
10. A process according to claim 9, further comprising the steps
of: recovering either or both of the (poly)alkylene glycol dialkyl
ether and the alcohol, both of which form as by-products in the
reaction between the olefin and the (poly)alkylene glycol; and
recycling the recovered either or both of the (poly)alkylene glycol
dialkyl ether and the alcohol to a system of the reaction between
the olefin and the (poly)alkylene glycol.
11. A process according to claim 9, further comprising the steps
of: recovering the resultant olefin phase and the resultant
(poly)alkylene glycol phase after the reaction; and separating the
(poly)alkylene glycol monoalkyl ether from the olefin phase.
12. A process according to claim 11, further comprising the step of
recovering either or both of the (poly)alkylene glycol dialkyl
ether and the alcohol, both of which form as by-products, from the
olefin phase after the reaction.
13. A process according to claim 9, further comprising the steps
of: recovering an unreacted residue of the olefin after the
reaction; and recycling the unreacted residue of the olefin to the
reaction with the (poly)alkylene glycol.
14. A process according to claim 9, further comprising the step of
recycling a (poly)alkylene glycol phase, resultant from the
reaction and including the catalyst, to the reaction with the
olefin.
15. A process according to claim 9, wherein a crystalline
metallosilicate is used as the catalyst.
16. A process according to claim 9, wherein: the (poly)alkylene
glycol monoalkyl ether is a (poly)alkylene glycol mono-higher-alkyl
ether; the olefin is a long chain olefin; the (poly)alkylene glycol
dialkyl ether is a (poly)alkylene glycol di-higher-alkyl ether; and
the alcohol is a higher alcohol.
Description
BACKGROUND OF THE INVENTION
[0001] A. Technical Field
[0002] The present invention relates to a production process for a
(poly)alkylene glycol monoalkyl ether.
[0003] B. Background Art
[0004] As to processes for producing a (poly)alkylene glycol
monoalkyl ether by reacting an olefin and a (poly)alkylene glycol,
for example, the following processes are disclosed: a process in
which strong acid cation-exchange resins are used as the catalyst
(e.g. Japanese Allowable Patent Publication (Kokoku) No. 57-35687
and Japanese Patent Application Publication (Kokai) No. 2-295941);
a process in which heteropolyacids are used as the catalyst
(Japanese Patent Application Publication (Kokai) No. 3-148233); and
a process in which benzenesulfonic acid or toluenesulfonic acid is
used as the catalyst (Japanese Allowable Patent Publication
(Kokoku) No. 61-51570).
[0005] However, where the strong acid cation-exchange resins, the
heteropolyacids, the benzenesulfonic acid, or the toluenesulfonic
acid is used as the catalyst, there are problems in that because
the (poly)alkylene glycol which is a raw material is a diatomic
alcohol, the reaction tends to involve a dehydration
polycondensation reaction or dehydration cyclization reaction of
the (poly)alkylene glycol itself as a side reaction to form water,
and this formed water tends to react upon the olefin to form an
alcohol as a by-product, so the resultant selectivity to the
(poly)alkylene glycol monoalkyl ether is extremely low. For
instance, examples of some preferred embodiments as set forth in
the Japanese Patent Application Publication (Kokai) No. 2-295941
disclose that when ethylene glycol and dodecene are reacted using
Nafion H (fluorine-containing strong acid ion-exchange resin), made
by E.I. Du Pont DE NEMOURS & Co., Ltd., as the catalyst to
produce ethylene glycol monododecyl ether, dodecanol forms as a
by-product in a proportion of 7 to 10 mol % of the ethylene glycol
monododecyl ether.
SUMMARY OF THE INVENTION
[0006] A. Objects of the Invention
[0007] An object of the present invention is to provide a process
for producing a (poly)alkylene glycol monoalkyl ether with high
selectivity.
[0008] B. Disclosure of the Invention
[0009] The present inventors diligently studied to attain the
above-mentioned object, and as a result, found that if a
crystalline metallosilicate is used as the catalyst, or if the
reaction between the olefin and the (poly)alkylene glycol is
carried out in the presence of an alcohol, the resultant
selectivity to the (poly)alkylene glycol monoalkyl ether is high,
in other words, that if a catalyst with high catalytic activity
such as the crystalline metallosilicate is used, not only can the
selectivity be raised, but also does the reaction rate become fast
to lead to the increase in the conversion, or if the alcohol which
will be a by-product is added into the reaction system, the side
reaction can be inhibited due to the principle of equilibrium
reaction.
[0010] By the way, the inventors further got the below-mentioned
two findings:
[0011] First, it was found that the addition reaction of the olefin
upon the (poly)alkylene glycol includes not only a reaction of the
formation of the (poly)alkylene glycol monoalkyl ether from the
(poly)alkylene glycol, but also a reaction of formation of a
(poly)alkylene glycol dialkyl ether. The activity of prior art
catalysts is low, and no prior art disclosed the formation of the
(poly)alkylene glycol dialkyl ether. However, it became clear that
where a high active catalyst such as the crystalline
metallosilicate is used, the (poly)alkylene glycol dialkyl ether
also forms, so the resultant selectivity of the (poly)alkylene
glycol monoalkyl ether is low. Therefore, it was found that when
the olefin and the (poly)alkylene glycol are reacted to produce the
(poly)alkylene glycol monoalkyl ether, it is effective to add the
(poly)alkylene glycol dialkyl ether to inhibit the formation
thereof as well.
[0012] Secondly, the crystalline metallosilicate has a problem in
that where it is used for a reaction, its catalytic activity
decreases with time. Thus, to solve this problem, the present
inventors found that if at least a portion of the used catalyst is
regenerated and then recycled as the catalyst for the reaction, the
stationary activity of the catalyst can be obtained. As a result,
the inventors completed the present invention.
[0013] That is to say, a process for producing a (poly)alkylene
glycol monoalkyl ether, according to a first embodiment of the
present invention, comprises the step of reacting a (poly)alkylene
glycol and an olefin in the presence of a catalyst, thus obtaining
the (poly)alkylene glycol monoalkyl ether, with the process being
characterized in that a crystalline metallosilicate is used as the
catalyst, and further characterized by further comprising the steps
of: regenerating at least a portion of the used catalyst; and
recycling the regenerated portion of the used catalyst as the
catalyst for the reaction between the (poly)alkylene glycol and the
olefin (herein, this production process is referred to as "first
production process").
[0014] In the first production process of the present invention, it
is preferable that the regeneration of the catalyst is carried out
by thermal treatment of the catalyst at 450.degree.C. or higher
under an oxygen-containing gas atmosphere. In addition, it is
preferable that the crystalline metallosilicate is a BEA type
metallosilicate. In addition, it is preferable that at least a
portion of a slurry containing the catalyst and an unreacted
residue of the (poly)alkylene glycol is extracted, and that the
catalyst is then recovered from the slurry to regenerate the
catalyst. In addition, it is preferable that when the catalyst is
recovered from the slurry, the (poly)alkylene glycol is also
recovered from the slurry by distillation under temperature
conditions of 180.degree.C. or lower, or that when the catalyst is
recovered from the slurry, the (poly)alkylene glycol is also
recovered from the slurry by distillation within 30 minutes. In
addition, it is preferable that a long chain olefin is used as the
olefin, when a (poly)alkylene glycol mono-higher-alkyl ether is
obtained as the (poly)alkylene glycol monoalkyl ether. In addition,
it is preferable that the regeneration of at least a portion of the
used catalyst is carried out after the catalyst is used for 0.02 to
100 hours for the reaction.
[0015] A process for producing a (poly)alkylene glycol monoalkyl
ether, according to a second embodiment of the present invention,
comprises the step of reacting an olefin and a (poly)alkylene
glycol in the presence of a catalyst, thus obtaining the
(poly)alkylene glycol monoalkyl ether, with the process being
characterized in that the reaction between the olefin and the
(poly)alkylene glycol is carried out in the presence of either or
both of a (poly)alkylene glycol dialkyl ether and an alcohol
(herein, this production process is referred to as "second
production process").
[0016] In addition, the second production process of the present
invention may be further characterized by further comprising the
steps of:
[0017] recovering either or both of the (poly)alkylene glycol
dialkyl ether and the alcohol, both of which form as by-products in
the reaction between the olefin and the (poly)alkylene glycol;
and
[0018] recycling the recovered either or both of the (poly)alkylene
glycol dialkyl ether and the alcohol to a system of the reaction
between the olefin and the (poly)alkylene glycol.
[0019] In addition, the second production process of the present
invention may be further characterized by further comprising the
steps of:
[0020] recovering the resultant olefin phase and the resultant
(poly)alkylene glycol phase after the reaction; and
[0021] separating the (poly)alkylene glycol monoalkyl ether from
the olefin phase.
[0022] In addition, the second production process of the present
invention may be further characterized by further comprising the
step of recovering either or both of the (poly)alkylene glycol
dialkyl ether and the alcohol, both of which form as by-products,
from the olefin phase after the reaction.
[0023] In addition, the second production process of the present
invention may be further characterized by further comprising the
steps of:
[0024] recovering an unreacted residue of the olefin after the
reaction; and
[0025] recycling the unreacted residue of the olefin to the
reaction with the (poly)alkylene glycol.
[0026] In addition, the second production process of the present
invention may be further characterized by further comprising the
step of recycling a (poly)alkylene glycol phase, resultant from the
reaction and including the catalyst, to the reaction with the
olefin.
[0027] In addition, the second production process of the present
invention may be further characterized in that a crystalline
metallosilicate is used as the catalyst.
[0028] In addition, the second production process of the present
invention may be further characterized in that: the (poly)alkylene
glycol monoalkyl ether is a (poly)alkylene glycol mono-higher-alkyl
ether; the olefin is a long chain olefin; the (poly)alkylene glycol
dialkyl ether is a (poly)alkylene glycol di-higher-alkyl ether; and
the alcohol is a higher alcohol.
[0029] These and other objects and the advantages of the present
invention will be more fully apparent from the following detailed
disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] FIG. 1 shows an example of flow charts of reaction
apparatuses with a batch type reactor.
[0031] FIG. 2 shows an example of flow charts of reaction
apparatuses with continuous vessel type reactors.
DETAILED DESCRIPTION OF THE INVENTION
[0032] Preferable examples of the olefin, as used in the present
invention, include hydrocarbons of 2 to 40, more preferably, 8 to
30, still more preferably, 10 to 20, in number of carbon atoms with
an ethylenically unsaturated bond. Among the olefins, particularly,
long chain olefins are preferable. When the long chain olefin is
used as the olefin, the resultant (poly)alkylene glycol monoalkyl
ether is a (poly)alkylene glycol mono-higher-alkyl ether, the
(poly)alkylene glycol dialkyl ether is a (poly)alkylene glycol
di-higher-alkyl ether, and the alcohol is a higher alcohol.
Preferable examples of the long chain olefin include hydrocarbons
of 8 to 30, more preferably, 10 to 20, in number of carbon atoms
with an ethylenically unsaturated bond.
[0033] Even if the olefins are branched ones, linear chain ones,
acyclic ones, cyclic ones, or mixtures thereof, they can be used
with no especial limitation. Considering the use for surfactants,
however, it is preferable that the olefin comprises an acyclic
olefin, more preferably, a linear chain olefin, as the main
component. Specific examples thereof include octene, decene,
dodecene, tetradecene, hexadecene, octadecene, icosene, docosene.
These olefins, of which the position of the unsaturated bond is
.alpha.-position, inner position, or both them, can be used with no
especial limitation. Of course, two or more olefins which are
different from each other with regard to the position of the
unsaturated bond can be used in combination. The process of the
reaction in the present invention involves a reaction in which the
olefin isomerizes with regard to the position of the unsaturated
bond. An inner olefin is generally thermodynamically more stable
than an .alpha.-olefin, and therefore, when the .alpha.-olefin is
used as a raw material, it gradually isomerizes to the inner olefin
during the reaction. The speed of the isomerization depends on the
reaction temperature or the type or amount of the catalyst.
[0034] Examples of the (poly)alkylene glycol, as used in the
present invention, include monoethylene glycol, diethylene glycol,
triethylene glycol, polyethylene glycol, monopropylene glycol,
dipropylene glycol, tripropylene glycol, polypropylene glycol,
1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol,
1,6-hexanediol, 1,4-cyclohexanemethanediol. These may be used
either alone or in combinations of two or more thereof.
[0035] Acid catalysts are suitable for the catalyst as used in the
present invention. Examples of thereof include: homogeneous
catalysts such as sulfuric acid, benzenesulfonic acid,
dodecylbenzenesulfonic acid, and heteropolyacids (e.g.
phosphotungstic acid, phosphomolybdic acid, silicotungstic acid,
silicomolybdic acid); acid ion-exchange resins; complex metal
oxides such as silica-alumina and titania-silica; and zeolite.
These catalysts may be used either alone or in combinations of two
or more thereof.
[0036] Among them, particularly, crystalline metallosilicates are
preferable. The crystalline metallosilicate is a regular porous
substance having a certain crystal structure, in other words, a
solid substance having many regular interstices or pores in the
structure and a large specific surface area.
[0037] Examples of the crystalline metallosilicate, as used in the
present invention, include crystalline aluminosilicate (which may
be commonly called zeolite) and compounds in which another metal
element is introduced into a crystal lattice in place of the Al
atom of the crystalline aluminosilicate. Specific examples of the
another metal element include B, Ga, In, Ge, Sn, P, As, Sb, Sc, Y,
La, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn. These may be used either
alone or in combinations of two or more thereof. Considering the
catalytic activity and the ease of the synthesis or availability,
crystalline aluminosilicate, crystalline ferrosilicate, crystalline
borosilicate, and crystalline gallosilicate are preferable, and
particularly, crystalline aluminosilicate is favorable.
[0038] Specific examples of the crystalline metallosilicate, as
used in the present invention, include those which have structures
such as MFI (e.g. ZSM-5), MEL (e.g. ZSM-11), BEA (e.g. .beta.-type
zeolite), FAU (e.g. Y-type zeolite), MOR (e.g. Mordenite), MTW
(e.g. ZSM-12), and LTL (e.g. Linde L), as described using IUPAC
codes in accordance with nomenclature by the Structure Commission
of the International Zeolite Association, and further, those which
have structures as disclosed in "ZEOLITES, Vol. 12, No. 5, 1992" or
"HANDBOOK OF MOLECULAR SIEVES, written by R. Szostak, published by
VAN NOSTRAND REINHOLD." These may be used either alone or in
combinations of two or more thereof. Among them, such as has a BEA
structure is particularly preferable, considering its excellent
catalytic activity.
[0039] A preferable example of the crystalline metallosilicate, as
used in the present invention, is such in which the atomic ratio of
the silicon atom to the metal atom, constituting the crystalline
metallosilicate, is in the range of 5 to 1,500, more preferably, 10
to 500. Where the atomic ratio of the silicon atom to the metal
atom is too small or too large, the catalytic activity is
unfavorably low.
[0040] The crystalline metallosilicate has an ion-exchangeable
cation outside the crystal lattice. Specific examples of such a
cation include H.sup.+, Li.sup.+, Na.sup.+, Rb.sup.+, Cs.sup.+,
Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Sc.sup.3+, Y.sup.3+,
La.sup.3+, R.sub.4N.sup.+, R.sub.4P.sup.+(R is H or alkyl).
Particularly, a crystalline metallosilicate in which the cation is
partially or entirely replaced with a hydrogen ion is favorable as
the catalyst in the present invention.
[0041] The crystalline metallosilicate, as used in the present
invention, can be synthesized by conventionally used synthesis
methods such as hydrothermal synthesis methods, specifically, by
methods as disclosed in Japanese Allowable Patent Publication
(Kokoku) No. 46-10064; U.S. Pat. No. 3,965,207; "The Journal of
Molecular Catalysis," Vol. 31, pp. 355-370 (published in 1985); and
Zeolites, Vol. 8, p. 46 (published in 1988). The crystalline
metallosilicate, for example, can be synthesized in the following
way: a composition comprising a silica source, a metal source, and
a quaternary ammonium salt such as a tetraethylammonium salt or
tetrapropylammonium salt is heated at a temperature of about 100 to
about 175.degree.C. until a crystal forms, and the resultant solid
product is then filtered off, washed with water, and dried, and
then calcined at 350-600.degree.C. Metallosilicates of different
crystal systems can be obtained by fitly adjusting raw materials or
synthesis conditions.
[0042] Examples of the aforementioned silica source include water
glass, silica sol, silica gel, and alkoxysilanes. Examples of the
aforementioned metal source include various inorganic or organic
metal compounds. Preferable examples of the metal compound include:
metal salts such as metal sulfates (e.g. Al.sub.2(SO.sub.4).sub.3),
metal nitrates (e.g. Fe(NO.sub.3).sub.3), and alkaline metal salts
of metal oxides (e.g. NaAlO.sub.2); metal halides such as metal
chlorides (e.g. TiCl.sub.4) and metal bromides (e.g. MgBr.sub.2);
and metal alkoxides (e.g. Ti(OC.sub.2H.sub.5).sub.4). The resultant
crystalline metallosilicate can be converted into an objective
cation matter by ion-exchange, if necessary. For example, an
H.sup.+type cation matter can be prepared in the following way: the
crystalline metallosilicate is mixed by stirring in an aqueous
solution of HCl, NH.sub.4Cl, or NH.sub.3 to exchange the cation
species with an H.sup.+type or NH.sub.4.sup.+type, and the
resultant solid product is then filtered off, washed with water,
and dried, and then calcined at 350-600.degree.C. Cation matters
other than the H.sup.+type can be prepared by carrying out the same
procedure as the above-mentioned one using an aqueous solution
containing an objective cation.
[0043] As to the crystalline metallosilicate, either crystalline
metallosilicates of sole crystal systems or crystalline
metallosilicates of combinations of various crystal systems may be
used.
[0044] The crystalline metallosilicate may be jointly used with
conventional catalysts such as sulfuric acid, heteropolyacids,
benzenesulfonic acid, and ion-exchange resins.
[0045] In the present invention, the catalyst may be used in any
form, and, for example, powdered ones, granular ones, or molded
matters of specific shapes can be used. In addition, where the
molded matter is used, examples of carriers or binders of the
molded matter include alumina, silica, and titania. In addition,
where a homogeneous catalyst is used as the catalyst, it can be
used in a dissolved state in a raw reaction material.
[0046] The (poly)alkylene glycol dialkyl ether, as used in the
second production process of the present invention, is resultant
from a further addition reaction of the olefin upon the
(poly)alkylene glycol monoalkyl ether, which is the objective
product in the second production process of the present invention,
or resultant from a condensation reaction between (poly)alkylene
glycol monoalkyl ethers, and is a substance as obtained as a
by-product when the olefin and the (poly)alkylene glycol are
reacted in the presence of a catalyst to produce the (poly)alkylene
glycol monoalkyl ether. The alcohol, as used in the second
production process of the present invention, is a substance as
obtained as a by-product by an addition reaction of a water content
in the reaction system upon the olefin when the olefin and the
(poly)alkylene glycol are reacted in the presence of a catalyst to
produce the (poly)alkylene glycol monoalkyl ether.
[0047] In the second production process of the present invention,
if either or both of the (poly)alkylene glycol dialkyl ether and
the alcohol, both of which form as by-products, are supplied to a
system of the reaction between the olefin and the (poly)alkylene
glycol, the (poly)alkylene glycol monoalkyl ether can be obtained
efficiently.
[0048] The reason why the (poly)alkylene glycol monoalkyl ether can
be obtained efficiently by supplying the (poly)alkylene glycol
dialkyl ether to the reaction system can be explained as follows:
It seems that between the olefin <=> the (poly)alkylene
glycol monoalkyl ether <=> the (poly)alkylene glycol dialkyl
ether, there are the following equilibrium relations:
OL+PAG<=>M (1)
OL+M<=>D (2)
M+M<=>D+PAG (3)
[0049] wherein: OL is the olefin, PAG is the (poly)alkylene glycol,
M is the (poly)alkylene glycol monoalkyl ether, and D is the
(poly)alkylene glycol dialkyl ether; and that the addition
reaction, the condensation reaction, and reverse reactions of them
run simultaneously. Thus, if the (poly)alkylene glycol dialkyl
ether is supplied to the reaction system, reverse reactions of (2)
and (3) above run, thus obtaining the (poly)alkylene glycol
monoalkyl ether. In addition, if the (poly)alkylene glycol dialkyl
ether, which forms as a by-product in the reaction between the
olefin and the (poly)alkylene glycol, is recovered and supplied
(recycled) to the next reaction to carry out the reaction,
substantially only the (poly)alkylene glycol monoalkyl ether can be
selectively obtained from the olefin and the (poly)alkylene
glycol.
[0050] The reason why the (poly)alkylene glycol monoalkyl ether can
be obtained efficiently by supplying the alcohol to the reaction
system can be explained as follows: It seems that between the
olefin <=> the alcohol, there is the following equilibrium
relation:
OL+H.sub.2O<=>AL (4)
[0051] wherein: OL is the olefin and AL is the alcohol; and that
the hydration reaction and the reverse reaction thereof run
simultaneously. Thus, if the alcohol is supplied to the reaction
system, the reverse reaction of (4) above runs, thus obtaining the
olefin that is a raw material. In addition, if the alcohol, which
forms as a by-product in the reaction between the olefin and the
(poly)alkylene glycol, is recovered and supplied (recycled) to the
next reaction to carry out the reaction, substantially only the
(poly)alkylene glycol monoalkyl ether can be selectively obtained
from the olefin and the (poly)alkylene glycol.
[0052] The reaction between the olefin and the (poly)alkylene
glycol in the present invention can be carried out either in the
presence of or in the absence of a solvent. Examples of the
solvent, as can be used, include nitromethane, nitroethane,
nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane,
benzene, toluene, xylene, hexane, cyclohexane, decane,
paraffin.
[0053] The reaction between the olefin and the (poly)alkylene
glycol in the present invention can be carried out in
conventionally used manners such as batch type reactions and flow
type reactions, and is not especially limited. The molar ratio
between the olefin and the (poly)alkylene glycol, which are raw
reaction materials, is not especially limited, but is preferably in
the range of 0.05 to 20, more preferably, 0.1 to 10, as the molar
ratio of the (poly)alkylene glycol to the olefin. The reaction
temperature is preferably in the range of 50 to 250.degree.C., more
preferably, 100 to 200.degree.C., and the reaction pressure may be
any of a reduced one, a normal one, and an increased one, but it is
preferably in the range from a normal pressure to 20
kg/cm.sup.2.
[0054] The respective amounts of the (poly)alkylene glycol dialkyl
ether and the alcohol, either or both of which are supplied to the
system of the reaction between the olefin and the (poly)alkylene
glycol in the second production process, is not especially limited.
The (poly)alkylene glycol dialkyl ether or the alcohol, both of
which form as by-products, may be recovered and accumulated, and
then supplied to the reaction system at once, or the (poly)alkylene
glycol dialkyl ether or the alcohol, resultant from the previous
reaction as by-products, may always be supplied to the next
reaction. When the flow type reaction is carried out to
continuously produce the (poly)alkylene glycol monoalkyl ether, it
is preferable that the (poly)alkylene glycol dialkyl ether or the
alcohol, both of which form as by-products, is continuously
recovered and always supplied by recycling to the reaction system.
The amount of the formation of the (poly)alkylene glycol dialkyl
ether or the alcohol, both of which form as by-products in the
reaction between the olefin and the (poly)alkylene glycol, depends
on factors such as the types or molar ratio of the olefin and the
(poly)alkylene glycol, the type of the catalyst as used, the
reaction temperature, or the reaction period of time, but the
amount is usually in the range of 0.0001 to 30 mol % of the olefin
which is a raw material. In addition, both the (poly)alkylene
glycol dialkyl ether and the alcohol substantially might not form
as by-products, depending on factors such as the type of the
catalyst or the types of the raw materials as used or reaction
conditions. Furthermore, either the (poly)alkylene glycol dialkyl
ether or the alcohol, both of which form as by-products, might be
recovered as a product. In these cases, it is enough for the
present invention to supply only either the (poly)alkylene glycol
dialkyl ether or the alcohol to the system of the reaction between
the olefin and the (poly)alkylene glycol.
[0055] Where a batch type reactor is used, the catalyst and the raw
materials are charged into the reactor, and the agitation is
carried out at a predetermined temperature under a predetermined
pressure, thus obtaining a mixture containing the objective
(poly)alkylene glycol monoalkyl ether. The amount of the catalyst,
as used, is not especially limited, but is preferably in the range
of 0.1 to 100 wt %, more preferably, 0.5 to 50 wt %, of the olefin
which is a raw material. The reaction period of time depends on
factors such as the reaction temperature, the amount of the
catalyst, or the ratio of the composition of the raw materials, but
is preferably in the range of 0.1 to 100 hours, more preferably,
0.5 to 30 hours.
[0056] Where a flow type reactor is used, the reaction can be
carried out in any of a fluidized bed manner, an entrained bed
manner, a fixed bed manner, and a stirred vessel manner. Reaction
conditions depend on factors such as the composition of the raw
materials, the concentration of the catalyst, or the reaction
temperature, but the liquid hourly space velocity (LHSV), namely,
the value as obtained by dividing the volume flow rate of the
flowing raw materials by the volume of the reactor, is preferably
in the range of 0.01 to 50 hr.sup.-1, more preferably, 0.1 to 20
hr.sup.-1.
[0057] In the first production process of the present invention, at
least a portion of the used catalyst is regenerated (preferably
after the catalyst is used for 0.02 to 100 hours for the reaction)
and then recycled as the catalyst for the reaction between the
(poly)alkylene glycol and the olefin. Where an unregenerated
portion of the catalyst is present, the regenerated portion of the
catalyst can be used in combination with the unregenerated portion
of the catalyst. The catalyst loses its activity with time, but if
at least a portion of the used catalyst is regenerated and then
recycled in the above-mentioned way, the stationary activity can be
obtained. The form of the recycling is not especially limited even
if it is either in a continuous manner or in a batch manner. The
preferable amount of the regeneration of the catalyst depends on
the amount of the catalyst as used in the reaction or on reaction
conditions, but is in the range of 0.5 wt % or more, further
preferably, 1 wt % or more, of the amount of the used catalyst in
the reaction. Where the amount of the regeneration is less than 0.5
wt %, the activity of the catalyst cannot be maintained, so the
reaction rate and the productivity are unfavorably deteriorated.
The upper limit of the amount of the regeneration is not especially
restricted, and the entirety of the catalyst may be regenerated,
but because the regeneration of the catalyst takes costs, the
amount of the regeneration is preferably suppressed to 50 wt % or
less, more preferably, 30 wt % or less.
[0058] In the first production process of the present invention,
the (poly)alkylene glycol and the olefin, which are raw materials,
merely dissolve into each other with a slight solubility, and in
many cases, therefore, the crystalline metallosilicate which is the
catalyst is mainly contained in the (poly)alkylene glycol phase,
and the (poly)alkylene glycol monoalkyl ether which is a product is
mainly contained in the olefin phase. Thus, in the first production
process of the present invention, it is preferable that: after the
reaction has ended, the (poly)alkylene glycol phase and the olefin
phase are separated from each other, and at least a portion of the
catalyst is extracted from the (poly)alkylene glycol phase
containing the catalyst (i.e. a slurry containing the catalyst and
an unreacted residue of the (poly)alkylene glycol), and then
regenerated, and then recycled to the next reaction between the
(poly)alkylene glycol and the olefin. The rest of the
(poly)alkylene glycol phase, from which at least a portion of the
catalyst is extracted, can be replenished with the (poly)alkylene
glycol, as consumed in the reaction or lost when extracting the
catalyst, and then recycled to the next reaction with the olefin.
In addition, an unreacted residue of the olefin and the objective
(poly)alkylene glycol monoalkyl ether can be recovered from the
olefin phase by separation methods such as distillation, and the
unreacted residue of the olefin can be then recycled to the next
reaction.
[0059] The method for recovering the catalyst for the regeneration
in the first production process is not especially limited, but the
catalyst can be recovered from the reaction liquid by methods such
as filtration, centrifugal separation, and drying. As is
aforementioned, the form of the use of the catalyst as used in the
first production process of the present invention is not especially
limited, but it is preferable for raising the reaction rate that
the catalyst is used in a state of a slurry in which the catalyst
is suspended as fine particles in the (poly)alkylene glycol phase.
Where such a form of the use is wanted, the separation of the
catalyst from the (poly)alkylene glycol phase by the filtration or
by the centrifugal separation involves the difficulty. In such a
case, a preferable method is a method in which the (poly)alkylene
glycol is distilled off from the slurry containing the
(poly)alkylene glycol and the catalyst, thereby separating and
recovering the catalyst. In such a method, the distilled
(poly)alkylene glycol can be recovered and then recycled to the
reaction system. When the (poly)alkylene glycol is distilled off
from the slurry, because the catalyst (crystalline metallosilicate)
is an acid catalyst, the catalyst runs unfavorable reactions such
as a condensation reaction of the (poly)alkylene glycol where
treated under high temperature conditions, and as a result, the
recovery ratio of the (poly)alkylene glycol decreases.
[0060] It is a condition for distilling off and recovering the
(poly)alkylene glycol in a high recovery ratio by inhibiting the
unfavorable reactions such as the condensation reaction that
temperature conditions fall within the range of 180.degree.C. or
lower, preferably, 150.degree.C. or lower. If a pressure under
which the (poly)alkylene glycol boils or a lower pressure is set
under the above-mentioned temperature conditions, the
(poly)alkylene glycol can be distilled off and recovered from the
slurry efficiently. Where the catalyst and the (poly)alkylene
glycol are recovered using a batch type evaporator or dryer, the
time of the contact between the catalyst and the (poly)alkylene
glycol (residence time) is so long that unfavorable reactions such
as the above-mentioned condensation reaction tend to occur. It is
especially preferable for inhibiting such reactions that the
above-mentioned temperature conditions are applied. Apparatuses for
recovering the catalyst or (poly)alkylene glycol are not limited to
the above-mentioned batch type evaporator or dryer, but examples
thereof include vacuum dryers such as centrifugal thin film types,
rotary drum types, conical ribbon types, belt types, and fluidized
bed types.
[0061] It is another condition for distilling off and recovering
the (poly)alkylene glycol in a high recovery ratio by inhibiting
the unfavorable reactions such as the condensation reaction that
the time, as needed for distilling off and recovering the
(poly)alkylene glycol, is shortened within 30 minutes, preferably,
within 15 minutes, more preferably, within 5 minutes, and still
more preferably, that the (poly)alkylene glycol is separated from
the catalyst and recovered by distilling off the (poly)alkylene
glycol almost in a moment. On such a occasion, it can be
conditioned that the temperature is 400.degree.C. or lower,
preferably, 300.degree.C. or lower, and that the pressure is normal
pressure or vacuum. Apparatuses for recovering the catalyst or
(poly)alkylene glycol are not especially limited, but examples
thereof include continuous type dryers such as centrifugal thin
film evaporators, instantaneous vacuum dryers, flash dryers, spray
dryers, and fluidized bed dryers.
[0062] In the first production process of the present invention,
methods for regenerating the catalyst are not especially limited,
but a preferable one is a method in which the catalyst is subjected
to thermal treatment under an oxygen-containing gas atmosphere. The
thermal treatment temperature is preferably 450.degree.C. or
higher, more preferably, 500.degree.C. or higher, still more
preferably, 550.degree.C. or higher. Where the thermal treatment
temperature is lower than 450.degree.C., a coke content remains in
the catalyst, so the catalytic activity is not restored. In
addition, the upper limit of the thermal treatment temperature is a
temperature at which the structure of the crystalline
metallosilicate is not destroyed, for example, generally
900.degree.C. or lower, preferably 800.degree.C. or lower, more
preferably 700.degree.C. or lower, still more preferably
650.degree.C. or lower. Apparatuses as used for the thermal
treatment not especially limited, but examples thereof include
calcination furnaces such as rotary kilns, box furnaces, fluidized
bed furnaces, roller-hearth kilns, mesh belt furnaces, and tray
pusher furnaces.
[0063] The used catalyst can be directly subjected to the thermal
treatment under an oxygen-containing gas atmosphere. Where the
catalyst contains a large amount of organic substances such as an
unrecovered portion of the (poly)alkylene glycol, however, the
thermal treatment under an oxygen-containing gas atmosphere might
cause ignition leading to high temperature, or the catalyst might
be deteriorated by the influence of steam as contained in a
combustion gas generating due to the combustion. In such a case, it
is preferable that: the recovered catalyst is once subjected to
thermal treatment in an inert gas to evaporate or decompose the
organic substances, thus removing them from the catalyst, and the
coke residue is then subjected to the above-mentioned thermal
treatment under an oxygen-containing gas atmosphere, thus
regenerating the catalyst.
[0064] In the second production process, the reaction liquid
usually separates into two phases because the (poly)alkylene glycol
and the olefin, which are raw materials, merely dissolve into each
other with a slight solubility. In addition, the catalyst (e.g.
crystalline metallosilicates) is mainly contained in the
(poly)alkylene glycol phase, and the (poly)alkylene glycol
monoalkyl ether, which is a product, and either or both of the
(poly)alkylene glycol dialkyl ether and the alcohol, both of which
are by-products, are mainly contained in the olefin phase.
Therefore, after the reaction has ended, the (poly)alkylene glycol
phase and the olefin phase are separated from each other, and the
objective (poly)alkylene glycol monoalkyl ether can be obtained
from the olefin phase by methods such as distillation and
extraction. In addition, an unreacted residue of the olefin can be
recovered, and then recycled to the next reaction with the
(poly)alkylene glycol. Furthermore, either or both of the
(poly)alkylene glycol dialkyl ether and the alcohol, both of which
are by-products, can be recovered and then, as aforementioned,
supplied and recycled to the system of the reaction between the
olefin and the (poly)alkylene glycol. The olefin generally has the
lowest boiling point of the unreacted olefin, the alcohol, the
(poly)alkylene glycol monoalkyl ether, and the (poly)alkylene
glycol dialkyl ether, and their boiling points become higher in
order of the alcohol, the (poly)alkylene glycol monoalkyl ether,
and the (poly)alkylene glycol dialkyl ether. Accordingly, the
unreacted olefin and the alcohol can be first recovered as
fractions by distillation, and the (poly)alkylene glycol monoalkyl
ether can be then recovered as the product, and the (poly)alkylene
glycol dialkyl ether can be either recovered as the distillation
bottom or purified by further distillation, and the unreacted
olefin and either or both of the (poly)alkylene glycol dialkyl
ether and the alcohol, both of which are by-products, can be
recycled to the system of the reaction between the olefin and the
(poly)alkylene glycol. In addition, a portion of the distillation
bottom may be discarded to purge impurities such as heavy, middle,
or light contents, and the rest may be supplied and recycled to the
system of the reaction between the olefin and the (poly)alkylene
glycol. In detail, the impurities in the olefin phase include:
light contents such as skeletal isomers of the olefin. condensation
decomposition products of the (poly)alkylene glycol (e.g. dioxane,
methyldioxolane); middle contents such as dimers of the olefin; or
heavy contents such as polymers of the olefin; and these impurities
can be separated and removed by fitly purifying the recovered
olefin or (poly)alkylene glycol dialkyl ether by methods such as
distillation.
[0065] Also in the second production process, the catalyst can be
separated from the (poly)alkylene glycol phase containing the
catalyst by methods such as centrifugal separation, filtration, and
drying, and then recycled to the next reaction. In addition, the
(poly)alkylene glycol can be recovered from the (poly)alkylene
glycol phase by methods such as distillation, and then recycled to
the next reaction with the olefin. It is preferable for simplifying
the process to replenish the (poly)alkylene glycol phase,
containing the catalyst, with the (poly)alkylene glycol, as
consumed by the reaction, and to then recycle the (poly)alkylene
glycol phase to the next reaction with the olefin. Where the
catalyst is gradually deactivated due to the reaction, at least a
portion of the catalyst can be extracted, and then regenerated or
newly replenished, and then supplied to the next reaction. In
addition, where impurities such as heavy contents or water
accumulate in the (poly)alkylene glycol phase, a portion of the
(poly)alkylene glycol phase may be extracted to purge the
impurities, and the rest may be recycled to the next reaction. The
heavy contents, such as high molecular polyalkylene glycol as
formed by condensation of the (poly)alkylene glycol, can be removed
by 1) a method in which a portion of the (poly)alkylene glycol
phase is purged or 2) a method in which when the catalyst is
recovered from the (poly)alkylene glycol phase and then
regenerated, the heavy contents are allowed to remain in the
catalyst and then removed by incineration during the regeneration
of the catalyst, and/or in which when the catalyst is recovered
from the (poly)alkylene glycol phase and then regenerated, the
heavy contents are removed from the recovered (poly)alkylene glycol
by purification by means such as distillation or adsorption. In
addition, water, as formed by dehydration condensation of the
(poly)alkylene glycol, can be removed by 1) a method in which a
portion of the (poly)alkylene glycol phase is purged or 2) a method
in which when the catalyst is recovered from the (poly)alkylene
glycol phase and then regenerated, water is removed from the
recovered (poly)alkylene glycol by purification by means such as
distillation or adsorption.
[0066] Next, an explanation is made about embodiments of the
present invention in accordance with the drawings. First, referring
to FIG. 1, an explanation is made about an embodiment of the
production process for the (poly)alkylene glycol monoalkyl ether
using a reaction apparatus having a batch type reactor as the
reactor.
[0067] As is shown in FIG. 1, the reaction apparatus comprises the
batch type reactor 1 and a distillation column 2. The batch type
reactor 1 is pressureproof and has a stirrer 1a and a heater 1b. A
raw material supply tube 4 and an extraction tube 5 are connected
to the batch type reactor 1. An upper part of the batch type
reactor 1 and a column bottom part of the distillation column 2 are
connected to each other through an introducing tube 3 such that a
gas generating from the batch type reactor 1 can be introduced into
the distillation column 2, and that a column bottom liquid in the
distillation column 2 can be returned to the batch type reactor 1.
An extraction tube 6 to extract distillates is connected to a
column top of the distillation column 2.
[0068] To begin with, a first reaction is carried out in the
absence of either or both of the (poly)alkylene glycol dialkyl
ether and the alcohol. The olefin, the (poly)alkylene glycol, and
the catalyst, which are raw reaction materials, and further the
solvent, if necessary, are charged into the batch type reactor 1
through the raw material supply tube 4. Next, the resultant
reaction liquid is heated while stirred to carry out the reaction
under conditions of a predetermined temperature and a predetermined
pressure, thus synthesizing the (poly)alkylene glycol monoalkyl
ether, when either or both of the (poly)alkylene glycol dialkyl
ether and the alcohol form as by-products. After the reaction has
ended, the stirrer is stopped, and the reaction liquid is allowed
to stand stationary and to thereby separate into the (poly)alkylene
glycol phase containing the catalyst (lower layer) and the olefin
phase containing the (poly)alkylene glycol monoalkyl ether (upper
layer). Thereafter, the (poly)alkylene glycol phase is extracted
from the batch type reactor 1 through the extraction tube 5. The
olefin phase remaining in the batch type reactor 1 is separated
into each component by batch distillation. While respective
pressures in the batch type reactor 1 and the distillation column
2, the temperature of the olefin phase remaining in the batch type
reactor 1, and the reflux ratio of the distillation column 2 are
controlled, each component present in the olefin phase is taken out
in ascendant order of the boiling point thereof as the distillate
from the column top of the distillation column 2 through the
extraction tube 6. The unreacted olefin and the alcohol as a
by-product are first recovered, and the (poly)alkylene glycol
monoalkyl ether is then recovered as a product. The (poly)alkylene
glycol dialkyl ether, which is a by-product, may be either
recovered by further distillation or allowed to remain as a
distillation bottom in the batch type reactor 1 and to be supplied
to the next batch type reaction. In addition, the distillation of
the olefin phase may be carried out using distillers (not drawn in
the figure) other than the distillation column 2.
[0069] Next, an explanation is made on second and subsequent
reactions. In the second and subsequent reactions, either or both
of the (poly)alkylene glycol dialkyl ether and the alcohol as
formed as by-products are supplied to the system of the reaction to
carry out the reactions. In addition, the unreacted olefin or the
(poly)alkylene glycol phase is recycled to carry out the reactions.
The unreacted olefin, the (poly)alkylene glycol phase containing
the catalyst, and either or both of the (poly)alkylene glycol
dialkyl ether and the alcohol as formed as by-products, all of
which are recovered from the previous batch type reaction, are used
as raw reaction materials, and further, the olefin and the
(poly)alkylene glycol as consumed in the previous reaction are
replenished to the raw reaction materials, which are then charged
into the batch type reactor 1 through the raw material supply tube
4. Where the (poly)alkylene glycol dialkyl ether was left as the
distillation bottom in the batch type reactor 1, the (poly)alkylene
glycol dialkyl ether does not need to be supplied through the raw
material supply tube 4. After the raw materials have been supplied,
the reaction is carried out under the same conditions as of the
previous reaction, and each component is separated and recovered
under the same conditions as of the previous reaction. By repeating
such a batch type reaction, either or both of the (poly)alkylene
glycol dialkyl ether and the alcohol, which are by-products, are
converted into the (poly)alkylene glycol monoalkyl ether, whereby
the (poly)alkylene glycol monoalkyl ether can be obtained with high
selectivity and high efficiency from the olefin and the
(poly)alkylene glycol. In addition, where impurities such as heavy
contents accumulate in the (poly)alkylene glycol phase or olefin
phase due to repeating the batch type reaction, the heavy contents
can be removed by purging a portion of the (poly)alkylene glycol
phase or a portion of the bottom resultant from the distillation of
the olefin phase.
[0070] Next, referring to FIG. 2, an explanation is made about an
embodiment of the production process for the (poly)alkylene glycol
monoalkyl ether using a reaction apparatus having a flow type
reactor as the reactor.
[0071] As is shown in FIG. 2, the reaction apparatus comprises
continuous vessel type reactors 11 and 12 and distillation columns
14 and 15. The continuous vessel type reactors 11 and 12 have
stirrers 11a and 12a and heaters 11b and 12b, respectively. A raw
material supply tube 20 is connected to the continuous vessel type
reactor 11, and an overflow type introducing tube 21 is connected
to an upper part of the continuous vessel type reactor 11. The
introducing tube 21 also serves as a raw material supply tube for
the continuous vessel type reactor 12. An overflow type introducing
tube 22 is connected to an upper part of the continuous vessel type
reactor 12 so as to be introduced into a liquid-liquid separator
(settler) 13. The liquid-liquid separator 13 and the distillation
column 14 are connected to each other through an introducing tube
23 such that a liquid of the upper layer as separated with the
liquid-liquid separator 13 can be introduced into the distillation
column 14. In addition, the liquid-liquid separator 13 and the raw
material supply tube 20 are connected to each other through an
introducing tube 24 such that a liquid of the lower layer as
separated with the liquid-liquid separator 13 can be returned to
the continuous vessel type reactor 11. An introducing tube 25 is
connected to the way of the introducing tube 24. A column bottom
part of the distillation column 14 is connected to the distillation
column 15 through an introducing tube 27 such that a column bottom
liquid in the distillation column 14 can be introduced into the
distillation column 15. In addition, a column top of the
distillation column 14 and the raw material supply tube 20 are
connected to each other through an introducing tube 26 such that
distillates from the distillation column 14 can be returned to the
continuous vessel type reactor 11. A column bottom part of the
distillation column 15 and the raw material supply tube 20 are
connected to each other through an introducing tube 29 such that a
column bottom liquid in the distillation column 15 can be returned
to the continuous vessel type reactor 11. An introducing tube 30 is
connected to the way of the introducing tube 29. An introducing
tube 28 is connected to a column top of the distillation column
15.
[0072] To begin with, the olefin, the (poly)alkylene glycol, and
the catalyst, which are raw reaction materials, and further the
solvent if necessary, are continuously charged into the continuous
vessel type reactor 11 through the raw material supply tube 20.
Next, the resultant reaction liquid is heated while stirred to
carry out the reaction under conditions of a predetermined
temperature and a predetermined pressure, thus synthesizing the
(poly)alkylene glycol monoalkyl ether, when either or both of the
(poly)alkylene glycol dialkyl ether and the alcohol form as
by-products. An overflow portion of the reaction liquid is
introduced into the continuous vessel type reactor 12 to further
carry out the reaction, and the resultant overflow portion is
introduced into the liquid-liquid separator 13. In the
liquid-liquid separator 13, the overflow portion is separated into
the (poly)alkylene glycol phase containing the catalyst (lower
layer) and the olefin phase containing the (poly)alkylene glycol
monoalkyl ether, the (poly)alkylene glycol dialkyl ether and the
alcohol (upper layer). Thereafter, the (poly)alkylene glycol phase
is extracted through the introducing tube 24 and, if need arises,
replenished with the (poly)alkylene glycol, as consumed in the
reaction, and then charged into the continuous vessel type reactor
11 through the raw material supply tube 20. In addition, if
necessary, a portion of the (poly)alkylene glycol phase may be
extracted from the introducing tube 25, as connected to the way of
the introducing tube 24, to regenerate a portion of the catalyst.
In such a case, the catalyst and the (poly)alkylene glycol are
recovered from the (poly)alkylene glycol phase as extracted from
the introducing tube 25, and the recovered catalyst is regenerated.
The regenerated catalyst and the recovered (poly)alkylene glycol
are supplied again to the continuous vessel type reactor 11 through
the raw material supply tube 20. Where impurities, such as heavy
contents and water which form due to side reactions such as
dehydration condensation, accumulate in the (poly)alkylene glycol
phase, the heavy contents can be removed to outside the system by
taking advantage of the extraction of at least a portion of the
(poly)alkylene glycol phase for the regeneration of the catalyst,
in other words, by purging a portion of the (poly)alkylene glycol
phase through the introducing tube 25. The olefin phase of the
upper layer in the liquid-liquid separator 13 is introduced into
the distillation column 14 through the introducing tube 23. While
the pressure in the distillation column 14, the temperature of the
olefin phase, and the reflux ratio of the distillation column 14
are controlled, low boiling point components present in the olefin
phase, namely, the unreacted olefin and the alcohol which is a
by-product, are extracted as distillates from the column top of the
distillation column 14 through the introducing tube 26. The olefin
and the alcohol, as extracted, are charged into the continuous
vessel type reactor 11 through the raw material supply tube 20
after, if need arises, replenished with the olefin as consumed in
the reaction. The (poly)alkylene glycol monoalkyl ether, which is a
distillation bottom of the distillation column 14, and the
(poly)alkylene glycol dialkyl ether, which is a by-product and a
distillation bottom of the distillation column 14, are introduced
into the distillation column 15 through the introducing tube 27.
While the pressure in the distillation column 15, the temperature
of the (poly)alkylene glycol monoalkyl ether phase, and the reflux
ratio of the distillation column 15 are controlled, the
(poly)alkylene glycol monoalkyl ether which is a low boiling point
component is extracted as a distillate from the column top of the
distillation column 15 through the introducing tube 28. The
(poly)alkylene glycol dialkyl ether, which is the distillation
bottom of the distillation column 15, is charged into the
continuous vessel type reactor 11 through the introducing tube 29
and further through the raw material supply tube 20. Where
impurities such as heavy contents accumulate in the (poly)alkylene
glycol dialkyl ether phase, the heavy contents can be removed by
purging a portion of the (poly)alkylene glycol dialkyl ether phase
through the introducing tube 30. In addition, where by-products,
such as skeletal isomers of the olefin. dimers of the olefin,
polymers of the olefin, and cyclization condensation products of
the (poly)alkylene glycol (e.g. dioxane, methyldioxolane),
accumulate in the olefin phase, the by-products can be removed, for
example, by fitly setting distillation columns and distilling off
the by-products (not drawn in the figure) or by purging a portion
of the distillation bottom liquid. In this way, when the
(poly)alkylene glycol and the olefin are reacted to produce the
(poly)alkylene glycol monoalkyl ether, if the crystalline
metallosilicate is used as the catalyst and if at least a portion
of the used catalyst is regenerated and then recycled as the
catalyst for the reaction between the (poly)alkylene glycol and the
olefin, the high activity of the catalyst can be maintained, and
the (poly)alkylene glycol monoalkyl ether can be obtained stably
and efficiently. Particularly, where the long chain olefin is used
as the olefin, if the above-mentioned flow type reaction is
repeated, either or both of the (poly)alkylene glycol
di-higher-alkyl ether and the higher alcohol, which are
by-products, are converted into the (poly)alkylene glycol
mono-higher-alkyl ether, whereby the (poly)alkylene glycol
mono-higher-alkyl ether can be obtained with high selectivity and
high efficiency from the long chain olefin and the (poly)alkylene
glycol.
[0073] The (poly)alkylene glycol monoalkyl ether as obtained in the
present invention is useful as a raw material for surfactants.
[0074] (Effects and Advantages of the Invention)
[0075] In the first production process of the present invention,
because the crystalline metallosilicate is used as the catalyst,
the (poly)alkylene glycol monoalkyl ether can be produced at a fast
reaction rate with high selectivity and high yield. In addition,
because at least a portion of the used catalyst is regenerated and
then recycled as the catalyst for the reaction, the stationary
activity of the catalyst can be obtained.
[0076] In addition, the second production process of the present
invention is capable of inhibiting the formation of by-products,
such as the (poly)alkylene glycol dialkyl ether and the alcohol,
and thereby producing the (poly)alkylene glycol monoalkyl ether
with high selectivity and high yield.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0077] Hereinafter, the present invention is more specifically
illustrated by the following examples of some preferred embodiments
in comparison with comparative examples not according to the
invention. However, the present invention is not limited to the
below-mentioned examples.
EXAMPLE 1
[0078] Ethylene glycol monododecyl ether was continuously produced
using a reaction apparatus as shown in FIG. 2. Stainless-steel-made
continuous vessel type reactors of 1,000 ml in capacity having a
stirrer and a band heater were used as the continuous vessel type
reactors 11 and 12. Overflow lines as shown by the introducing
tubes 21 and 22 were set to the continuous vessel type reactors 11
and 12, and an arrangement was made such that the reaction liquid
could run from the continuous vessel type reactor 11 to the
continuous vessel type reactor 12 and then to the liquid-liquid
separator 13 depending on a supply rate of the raw materials as
supplied through the raw material supply tube 20. A 15-stage
Oldershaw type distillation column with an inner diameter of 32 mm
.phi. was used as the distillation column 14, and the introducing
tube 23 was connected to the fifth stage from the column top. A
reflux device (not drawn in the figure) was set on the column top
of the distillation column 14. In addition, a preheater (not drawn
in the figure) was set near a connecting part between the
introducing tube 23 and the distillation column 14 to heat the
reaction liquid as supplied from the introducing tube 23 to the
distillation column 14. A packed column, which was made of
stainless steel and had an inner diameter of 20 mm .phi. and a
height of 500 mm, was used as the distillation column 15, and
stainless-steel-made Dixon packing of 1.5 mm .phi. was used as the
packing. In addition, a reflux device (not drawn in the figure) was
set on the column top of the distillation column 15. The
introducing tube 27 was connected to a central portion of the
distillation column 15, and a preheater (not drawn in the figure)
was set near a connecting part to heat the reaction liquid as
supplied from the introducing tube 27 to the distillation column
15. In addition, vacuum devices were set to the distillation
columns 14 and 15 respectively to carry out the distillation under
vacuum.
[0079] A mixture of 268 g of 1-dodecene, 298 g of monoethylene
glycol, and 32.7 g of BEA type zeolite (trade name: VALFOR CP
811BL-25, atomic ratio of Si to Al: 12.5, specific surface area:
750 m.sup.2/g, hereinafter abbreviated as catalyst), made of PQ
Co., Ltd., as the catalyst was charged into each of the continuous
vessel type reactors 11 and 12, and the stirrers were run at a
revolution number of 600 rpm. The temperature inside the reactors
was elevated to 150.degree.C., and thereafter, this temperature was
maintained. The raw materials and the catalyst were supplied from
the raw material supply tube 20 to the continuous vessel type
reactor 11 at supply rates of 268 g/hr for 1-dodecene, 298 g/hr for
monoethylene glycol, and 32.7 g/hr for the catalyst to initiate the
reaction, wherein the catalyst was suspended into monoethylene
glycol before supplied. The reaction liquid was transferred to the
liquid-liquid separator 13 through the introducing tube 22 and
separated into a monoethylene glycol phase containing the catalyst
and an olefin phase containing monoethylene glycol monododecyl
ether. The monoethylene glycol phase was recycled to the continuous
vessel type reactor 11 through the introducing tube 24, when 5 wt %
of a flow rate was purged from the introducing tube 25 to outside
the system. On the other hand, the olefin phase was supplied to the
distillation column 14 through the introducing tube 23. Operational
conditions of the distillation column 14 were as follows: column
top pressure=10 mmHg, column bottom temperature=185.degree.C.,
column top temperature=87.degree.C., reflux ratio=3. The main
distillate from the distillation column 14 was unreacted and
isomerized dodecene, and was recycled to the reactor 11 through the
introducing tube 26. The distillation residue of the distillation
column 14 was supplied to the distillation column 15 through the
introducing tube 27. Operational conditions of the distillation
column 15 were as follows: column top pressure=2 mmHg, column
bottom temperature=228.degree.C., column top
temperature=126.degree.C., reflux ratio=0.5. The main distillate
from the distillation column 15 was objective monoethylene glycol
monododecyl ether, which was recovered as a product through the
introducing tube 28. The main distillation residue of the
distillation column 15 was monoethylene glycol didodecyl ether,
which was recycled to the continuous vessel type reactor 11 through
the introducing tube 29. In this example, no purge of a portion of
the distillation residue of the distillation column 15 through the
introducing tube 30 was carried out. After the initiation of the
reaction, the respective amounts of the new raw materials
(1-dodecene and monoethylene glycol) and the new catalyst, as
supplied from the raw material supply tube 20, were controlled
depending on the respective flow rates of the recovered raw
materials and catalyst, as recycled through the introducing tubes
24, 26, and 29, such that the composition of the raw materials as
supplied to the continuous vessel type reactor 11 could be 3/1 as
the molar ratio of monoethylene glycol/dodecene, 10 wt % as the
amount of the catalyst in the monoethylene glycol phase, and 1
hr.sup.-1 as the liquid hourly space velocity (LHSV) as the flow
rate of the supplied liquid in the reactor 11.
[0080] The monoethylene glycol phase, which contained the catalyst
and had been continuously purged from the introducing tube 25 to
outside the system, was collected into vessels every twelve hours.
This purged liquid containing the catalyst was poured onto a flat
type evaporating dish to evaporate most of monoethylene glycol with
a vacuum dryer, whereby the catalyst was dried until solidified,
and the catalyst was then regenerated by calcining it for 3 hours
at 600.degree.C. under an air atmosphere in a muffle furnace. When
the regenerated catalyst was obtained for the first time after the
initiation of the reaction (about 24 hours after the initiation of
the reaction), a new lot of the catalyst as supplied from the raw
material supply tube 20 was switched to the regenerated catalyst,
and since then, the operation of the continuous reaction apparatus
was continued using the regenerated catalyst.
[0081] Two hundred hours after the initiation of the operation of
the continuous reaction apparatus under the above-mentioned
operational conditions, the respective amounts of 1-dodecene,
monoethylene glycol, and the regenerated catalyst, as newly
supplied to the raw material supply tube 20, were 24.8 g/hr, 23.3
g/hr, and 1.63 g/hr. In addition, the amount of the product as
recovered through the introducing tube 28 was 33.4 g/hr. As a
result of the analysis of this product by gas chromatography, the
product contained dodecanol in a proportion of 0.30 wt % and
diethylene glycol monododecyl ether in a proportion of 1.2 wt %. At
this time, the flow rate of the recycled liquid running through the
introducing tube 29 was 23.1 g/hr. The flow rate of the recycled
liquid running through the introducing tube 26 was 223.5 g/hr, and
this recycled liquid contained dodecanol in a proportion of 0.13 wt
%. The total yield of ethylene glycol monododecyl ether and
diethylene glycol monododecyl ether, relative to 1-dodecene as
supplied, was 98 mol %.
[0082] Five hundred hours after the subsequent continuation of the
operation, the amount of the product as recovered through the
introducing tube 28 was 33.2 g/hr, and as a result of the analysis
of this product by gas chromatography, the product contained
dodecanol in a proportion of 0.31 wt % and diethylene glycol
monododecyl ether in a proportion of 1.4 wt %. At this time, the
total yield of ethylene glycol monododecyl ether and diethylene
glycol monododecyl ether, relative to 1-dodecene as supplied, was
98 mol %.
COMPARATIVE EXAMPLE 1
[0083] The continuous reaction apparatus was operated to produce
monoethylene glycol monododecyl ether in the same way as of Example
1 except that no purge from the introducing tube 25 was carried
out, and that no addition of the new or regenerated catalyst from
the raw material supply tube 20 was carried out. One hundred hours
after the initiation of the reaction, the amount of the product as
recovered through the introducing tube 28 was 30.0 g/hr, and 200
hours after the initiation of the reaction, the amount of the
product as recovered through the introducing tube 28 reduced to
11.4 g/hr. Thereafter, because the amount of the formation of
monoethylene glycol monododecyl ether greatly reduced, the
continuous reaction apparatus could not stably be operated.
[0084] <Recovery of the (poly)alkylene glycol>
REFERENTIAL EXAMPLE 1
[0085] A mixture of 10.0 g of BEA type zeolite (trade name: VALFOR
CP 811BL-25, atomic ratio of Si to Al: 12.5, specific surface area:
750 m.sup.2/g, hereinafter abbreviated as catalyst), made of PQ
Co., Ltd., as the catalyst and 90.0 g of monoethylene glycol was
charged into a 200-ml eggplant-shaped flask, which was then set to
a rotary evaporator as equipped with a vacuum device and an oil
bath for heating. The oil bath was set at 180.degree.C., and the
eggplant-shaped flask was then immersed into the oil bath, and the
evaporator was then rotated. Thereafter, the vacuum device was run
and controlled to a pressure under which a distillate could be
obtained. The operation was ended when about 50 g of distillate was
collected. A slurry, which remained in the eggplant-shaped flask
and contained the catalyst, was filtered off with a membrane
filter, thus obtaining a bottom liquid. Each of the bottom liquid
and the distillate was analyzed by gas chromatography to determine
the contents of by-products other than monoethylene glycol. Results
are shown in Table 1.
REFERENTIAL EXAMPLES 2 AND 3
[0086] The recovery of monoethylene glycol was carried out in the
same way as of Referential Example 1 except that the temperature of
the oil bath was 150.degree.C. or 120.degree.C. Results are shown
in Table 1.
REFERENTIAL EXAMPLE 4
[0087] The recovery of monoethylene glycol was carried out in the
same way as of Referential Example 1 except that the temperature of
the oil bath was 200.degree.C., and that the pressure was normal
pressure. Results are shown in Table 1.
1 TABLE 1 By-product content (wt %) Recovery Distillate Botton
liquid Referential temperature Pressure Methyl- Diethylene
Diethylene Triethylene Example (.degree. C.) (mmHg) dioxolane
Dioxane glycol glycol glycol 1 180 400 0.7 0.3 0.2 1.0 0.1 2 150
150 0.1 0.0 0.0 0.2 0.0 3 120 40 0.0 0.0 0.0 0.1 0.0 4 200 760 5.9
7.3 0.8 8.4 0.7
REFERENTIAL EXAMPLE 5
[0088] The separation and recovery of the catalyst and monoethylene
glycol from the mixed slurry of the catalyst and monoethylene
glycol was carried out using an instantaneous vacuum dryer (trade
name: CRUX System, made by Hosokawa Mikron Co., Ltd.) as the dryer.
The instantaneous vacuum dryer comprises: a heating tube consisting
of a stainless steel pipe (inner diameter: 8 mm, length: 8 m); a
collector; a bag filter; and a condenser. The heating tube is
covered with a jacket such that an outer wall of the heating tube
can be heated by supplying steam or a heating medium into the
jacket. An end of the heating tube is connected to the collector,
and the bag filter is set on an upper part of the collector and
further connected to the condenser. Respective temperatures of the
heating tube, the collector, the bag filter, and the condenser can
be managed independently of each other. The condenser is further
connected to a vacuum pump such that respective pressures of the
condenser and the collector can be controlled. The mechanism is as
follows: the slurry, in which solid particles are dispersed in the
liquid, is supplied from an end of the heating tube using a
metering pump, thus thermally evaporating the liquid with the
heating tube as well as drying the solid particles with the heating
tube, and the evaporated gas is led to the condenser through the
bag filter and then liquefied, thus recovering the liquid, and the
dried solid particles are collected with the collector.
[0089] Operational conditions of the instantaneous vacuum dryer
were set as follows: the outer wall temperature of the heating tube
was 225.degree.C., the temperatures of the collector and the bag
filter were both 130.degree.C., the temperature of the condenser
was 1.degree.C., and the pressures of the collector and the
condenser were both 10 mmHg. A slurry was obtained by mixing 2.0 kg
of the catalyst (BEA type zeolite made by PQ Co., Ltd.), as used in
Referential Example 1, and 18.0 kg of monoethylene glycol. This
slurry was supplied to the heating tube at a rate of 12.5 kg/hr
using the metering pump. Slightly later than the initiation of the
supply, a powder began to be collected into the collector, and a
condensate began to distill into the condenser. After the entirety
of the slurry had been supplied, the operation of the instantaneous
vacuum dryer was stopped, and the recovered powder and condensate
were taken out, and the weights thereof were measured. As a result,
the recovered powder weighed 17.4 kg, and the recovered condensate
weighed 2.5 kg. The recovered powder was subjected to
thermogravimetric analysis to measure the catalyst content
(nonvolatile content). As a result, the catalyst content was 80.0
wt %. The recovered condensate was analyzed by gas chromatography
to determine the contents of by-products other than monoethylene
glycol. As a result, the contents of the by-products in the
condensate were 0.09 wt % for methyldioxolane, 0.16 wt % for
dioxane, and 0.10 wt % for diethylene glycol.
[0090] <Regeneration of the catalyst>
REFERENTIAL EXAMPLE 6
[0091] The monoethylene glycol phase, which contained the catalyst
and had been continuously purged from the introducing tube 25 to
outside the system in Example 1, was collected. This purged liquid
containing the catalyst was poured onto a flat type evaporating
dish to evaporate most of monoethylene glycol under conditions of
150.degree.C. and 200 mmHg with a vacuum dryer, whereby the
catalyst was dried until solidified, and the catalyst was then
calcined for 3 hours at 500.degree.C. under an air atmosphere in a
muffle furnace. The calcined catalyst was pale yellow, and as a
result of organic elemental analysis thereof, the carbon content in
the calcined catalyst was only 0.1 wt %.
REFERENTIAL EXAMPLE 7
[0092] The regeneration of the catalyst was carried out in the same
way as of Referential Example 6 except that the calcination
temperature was 600.degree.C. The calcined catalyst was white, and
as a result of organic elemental analysis thereof, no carbon was
detected.
REFERENTIAL EXAMPLE 8
[0093] The regeneration of the catalyst was carried out in the same
way as of Referential Example 6 except that the calcination
temperature was 400.degree.C. The calcined catalyst was black, and
as a result of organic elemental analysis thereof, the carbon
content in the calcined catalyst was 1.2 wt %.
EXAMPLE 2
[0094] Ethylene glycol monododecyl ether was continuously produced
using a reaction apparatus as shown in FIG. 2. Stainless-steel-made
continuous vessel type reactors of 1,000 ml in capacity having a
stirrer and a band heater were used as the continuous vessel type
reactors 11 and 12. Overflow lines as shown by the introducing
tubes 21 and 22 were set to the continuous vessel type reactors 11
and 12, and an arrangement was made such that the reaction liquid
could run from the continuous vessel type reactor 11 to the
continuous vessel type reactor 12 and then to the liquid-liquid
separator 13 depending on a supply rate of the raw materials as
supplied through the raw material supply tube 20. A 15-stage
Oldershaw type distillation column with an inner diameter of 32 mm
.phi. was used as the distillation column 14, and the introducing
tube 23 was connected to the fifth stage from the column top. A
reflux device (not drawn in the figure) was set on the column top
of the distillation column 14. In addition, a preheater (not drawn
in the figure) was set near a connecting part between the
introducing tube 23 and the distillation column 14 to heat the
reaction liquid as supplied from the introducing tube 23 to the
distillation column 14. A packed column, which was made of
stainless steel and had an inner diameter of 20 mm .phi. and a
height of 500 mm, was used as the distillation column 15, and
stainless-steel-made Dixon packing of 1.5 mm .phi. was used as the
packing. In addition, a reflux device (not drawn in the figure) was
set on the column top of the distillation column 15. The
introducing tube 27 was connected to a central portion of the
distillation column 15, and a preheater (not drawn in the figure)
was set near a connecting part to heat the reaction liquid as
supplied from the introducing tube 27 to the distillation column
15. In addition, vacuum devices were set to the distillation
columns 14 and 15 respectively to carry out the distillation under
vacuum.
[0095] A mixture of 268 g of 1-dodecene, 298 g of monoethylene
glycol, and 32.7 g of BEA type zeolite (trade name: VALFOR CP
811BL-25, atomic ratio of Si to Al: 12.5, specific surface area:
750 m.sup.2/g, hereinafter abbreviated as catalyst), made of PQ
Co., Ltd., as the catalyst was charged into each of the continuous
vessel type reactors 11 and 12, and the stirrers were run at a
revolution number of 600 rpm. The temperature inside the reactors
was elevated to 150.degree.C., and thereafter, this temperature was
maintained. The raw materials and the catalyst were supplied from
the raw material supply tube 20 to the continuous vessel type
reactor 11 at supply rates of 268 g/hr for 1-dodecene, 298 g/hr for
monoethylene glycol, and 32.7 g/hr for the catalyst to initiate the
reaction, wherein the catalyst was suspended into monoethylene
glycol before supplied. The reaction liquid was transferred to the
liquid-liquid separator 13 through the introducing tube 22 and
separated into a monoethylene glycol phase containing the catalyst
and an olefin phase containing monoethylene glycol monododecyl
ether. The monoethylene glycol phase was recycled to the continuous
vessel type reactor 11 through the introducing tube 24, when 5 wt %
of a flow rate was purged from the introducing tube 25 to outside
the system. On the other hand, the olefin phase was supplied to the
distillation column 14 through the introducing tube 23. Operational
conditions of the distillation column 14 were as follows: column
top pressure=10 mmHg, column bottom temperature=185.degree.C.,
column top temperature=87.degree.C., reflux ratio=3. The main
distillate from the distillation column 14 was unreacted and
isomerized dodecene, and was recycled to the reactor 11 through the
introducing tube 26. The distillation residue of the distillation
column 14 was supplied to the distillation column 15 through the
introducing tube 27. Operational conditions of the distillation
column 15 were as follows: column top pressure=2 mmHg, column
bottom temperature=228.degree.C., column top
temperature=126.degree.C., reflux ratio=0.5. The main distillate
from the distillation column 15 was objective monoethylene glycol
monododecyl ether, which was recovered as a product through the
introducing tube 28. The main distillation residue of the
distillation column 15 was monoethylene glycol didodecyl ether,
which was recycled to the continuous vessel type reactor 11 through
the introducing tube 29. In this example, no purge of a portion of
the distillation residue of the distillation column 15 through the
introducing tube 30 was carried out. After the initiation of the
reaction, the respective amounts of the new raw materials
(1-dodecene and monoethylene glycol) and the new catalyst, as
supplied from the raw material supply tube 20, were controlled
depending on the respective flow rates of the recovered raw
materials and catalyst, as recycled through the introducing tubes
24, 26, and 29, such that the composition of the raw materials as
supplied to the continuous vessel type reactor 11 could be 3/1 as
the molar ratio of monoethylene glycol/dodecene, 10 wt % as the
amount of the catalyst in the monoethylene glycol phase, and 1
hr.sup.-1 as the liquid hourly space velocity (LHSV) as the flow
rate of the supplied liquid in the reactor 11.
[0096] Two hundred hours after the initiation of the operation of
the continuous reaction apparatus under the above-mentioned
operational conditions, the respective amounts of 1-dodecene,
monoethylene glycol, and the catalyst, as newly supplied to the raw
material supply tube 20, were 24.8 g/hr, 23.3 g/hr, and 1.63 g/hr.
In addition, the amount of the product as recovered through the
introducing tube 28 was 33.4 g/hr. As a result of the analysis of
this product by gas chromatography, the product contained dodecanol
in a proportion of 0.30 wt % and diethylene glycol monododecyl
ether in a proportion of 1.2 wt %. At this time, the flow rate of
the recycled liquid running through the introducing tube 29 was
23.1 g/hr. The flow rate of the recycled liquid running through the
introducing tube 26 was 223.5 g/hr, and this recycled liquid
contained dodecanol in a proportion of 0.13 wt %. The total yield
of ethylene glycol monododecyl ether and diethylene glycol
monododecyl ether, relative to 1-dodecene as supplied, was 98 mol
%.
[0097] Five hundred hours after the subsequent continuation of the
operation, the amount of the product as recovered through the
introducing tube 28 was 33.2 g/hr, and as a result of the analysis
of this product by gas chromatography, the product contained
dodecanol in a proportion of 0.31 wt % and diethylene glycol
monododecyl ether in a proportion of 1.4 wt %. At this time, the
total yield of ethylene glycol monododecyl ether and diethylene
glycol monododecyl ether, relative to 1-dodecene as supplied, was
98 mol %.
EXAMPLE 3
[0098] Ethylene glycol monotetradecyl ether was continuously
produced using the same reaction apparatus as of Example 2. A
mixture of 291 g of 1-tetradecene, 276 g of monoethylene glycol,
and 30.7 g of BEA type zeolite (trade name: VALFOR CP 811BL-25,
atomic ratio of Si to Al: 12.5, specific surface area: 750
m.sup.2/g, hereinafter abbreviated as catalyst), made of PQ Co.,
Ltd., as the catalyst was charged into each of the reactors 11 and
12, and the stirrers were run at a revolution number of 600 rpm.
The temperature inside the reactors was elevated to 150.degree.C.,
and thereafter, this temperature was maintained. The raw materials
and the catalyst were supplied from the raw material supply tube 20
to the continuous vessel type reactor 11 at supply rates of 291
g/hr for 1-tetradecene, 276 g/hr for monoethylene glycol, and 30.7
g/hr for the catalyst to initiate the reaction. The subsequent
reaction operation was carried out in the same way as of Example 2,
wherein operational conditions of the distillation column 14 were
as follows: column top pressure=10 mmHg, column bottom
temperature=210.degree.C., column top temperature=120.degree.C.,
reflux ratio=3, and operational conditions of the distillation
column 15 were as follows: column top pressure=1 mmHg, column
bottom temperature=240.degree.C., column top
temperature=145.degree.C., reflux ratio=0.5.
[0099] After the initiation of the reaction, in the same way as of
Example 2, the respective amounts of the new raw materials and
catalyst as supplied from the raw material supply tube 20 were
controlled depending on the respective flow rates of the recovered
raw materials and catalyst, as recycled through the introducing
tubes 24, 26, and 29, such that the composition of the raw
materials as supplied to the continuous vessel type reactor 11
could be 3/1 as the molar ratio of monoethylene glycol/tetradecene,
10 wt % as the amount of the catalyst in the monoethylene glycol
phase, and 1 hr.sup.-1 as the liquid hourly space velocity (LHSV)
as the flow rate of the supplied liquid in the reactor 11.
[0100] Two hundred hours after the initiation of the operation of
the continuous reaction apparatus under the above-mentioned
operational conditions, the respective amounts of 1-tetradecene,
monoethylene glycol, and the catalyst, as newly supplied to the raw
material supply tube 20, were 23.3 g/hr, 20.6 g/hr, and 1.53 g/hr.
In addition, the amount of the product as recovered through the
introducing tube 28 was 30.0 g/hr. As a result of the analysis of
this product by gas chromatography, the product contained
tetradecanol in a proportion of 0.33 wt % and diethylene glycol
monotetradecyl ether in a proportion of 1.4 wt %. At this time, the
flow rate of the recycled liquid running through the introducing
tube 29 was 20.2 g/hr. The flow rate of the recycled liquid running
through the introducing tube 26 was 250.7 g/hr, and this recycled
liquid contained tetradecanol in a proportion of 0.12 wt %. The
total yield of ethylene glycol monotetradecyl ether and diethylene
glycol monotetradecyl ether, relative to 1-tetradecene as supplied,
was 97 mol %.
[0101] Five hundred hours after the subsequent continuation of the
operation, the amount of the product as recovered through the
introducing tube 28 was 29.9 g/hr, and as a result of the analysis
of this product by gas chromatography, the product contained
tetradecanol in a proportion of 0.36 wt % and diethylene glycol
monotetradecyl ether in a proportion of 1.6 wt %. At this time, the
total yield of ethylene glycol monotetradecyl ether and diethylene
glycol monotetradecyl ether, relative to 1-tetradecene as supplied,
was 97 mol %.
[0102] Various details of the invention may be changed without
departing from its spirit not its scope. Furthermore, the foregoing
description of the preferred embodiments according to the present
invention is provided for the purpose of illustration only, and not
for the purpose of limiting the invention as defined by the
appended claims and their equivalents.
* * * * *