U.S. patent application number 09/882339 was filed with the patent office on 2002-01-17 for method for manufacturing dialkyl carbonate.
Invention is credited to Kimura, Takato, Shimoda, Tomoaki, Tanaka, Masahide.
Application Number | 20020007087 09/882339 |
Document ID | / |
Family ID | 27481392 |
Filed Date | 2002-01-17 |
United States Patent
Application |
20020007087 |
Kind Code |
A1 |
Kimura, Takato ; et
al. |
January 17, 2002 |
Method for manufacturing dialkyl carbonate
Abstract
The specification describes a method for manufacturing dialkyl
carbonate by reacting carbon monoxide, oxygen and alcohol in the
presence of a catalyst. The catalyst is produced by reacting
together ingredients including a cupric halide and an alkoxide
compound of a group III through VII metal.
Inventors: |
Kimura, Takato; (Ichihara
City, JP) ; Shimoda, Tomoaki; (Ichihara City, JP)
; Tanaka, Masahide; (Ichihara City, JP) |
Correspondence
Address: |
Frank A. Smith
GE Plastics
One Plastics Avenue
Pittsfield
MA
01201
US
|
Family ID: |
27481392 |
Appl. No.: |
09/882339 |
Filed: |
June 14, 2001 |
Current U.S.
Class: |
568/300 ;
528/196 |
Current CPC
Class: |
C07C 68/01 20200101;
C07C 68/01 20200101; C07C 69/96 20130101; C07C 69/96 20130101; C07C
68/01 20200101 |
Class at
Publication: |
568/300 ;
528/196 |
International
Class: |
C07C 001/00; C08G
064/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 28, 2000 |
JP |
2000-195029 |
Jun 28, 2000 |
JP |
2000-195030 |
Jun 28, 2000 |
JP |
2000-195031 |
Jun 28, 2000 |
JP |
2000-195032 |
Claims
What is claimed is:
1. Method for manufacturing dialkyl carbonate, which method
comprises reacting together carbon monoxide, oxygen and alcohol in
the presence of a catalyst, which catalyst is produced by combining
together ingredients comprising a cupric halide and an alkoxide
comound of a metal selected from groups III through VIII of the
periodic table.
2. The method for manufacturing dialkyl carbonate according to
claim 1, wherein the catalyst further comprises a compound selected
from the group consisting of an alkali metal alkoxide, an alkaline
earth metal alkoxide, a quaternary ammonium alkoxide having formula
(1), R.sup.1R.sup.2R.sup.3R.sup.4NOR.sup.5 (1) and a quarternary
phosphonium alkoxide having formula (2),
R.sup.1R.sup.2R.sup.3R.sup.4POR.sup.5 (2) where R.sup.1-R.sup.4 may
be the same or different and denote hydrogen atoms or hydrocarbon
groups having 1-20 carbon atoms, and R.sup.5 denotes a hydrocarbon
group having 1-20 carbon atoms.)
3. The method for manufacturing dialkyl carbonate according to
claim 1, wherein the aforementioned alkoxide compound of a metal
from groups III through VIII of the periodic table is used in an
amount of 0.05-2.0 mol with respect to the cupric halide.
4. The method for manufacturing dialkyl carbonate according to
claim 2, wherein the aforementioned halide of a metal from groups
III through VIII of the periodic table is used in the amount of
0.05-2.0 mol with respect to the cupric halide.
5. The method for manufacturing dialkyl carbonate, which method
comprises reacting together carbon monoxide, oxygen, and alcohol in
the presence of a catalyst, which catalyst produced by combining
together ingredients comprising (I) a copper halide, and (II) an
alkaline earth metal halide.
6. The method for manufacturing dialkyl carbonate according to
claim 5, wherein the copper halide compound is cuprous
chloride.
7. The method for manufacturing dialkyl carbonate according to
claims 5, wherein the alkaline earth metal halide is magnesium
chloride or barium chloride.
8. The method for manufacturing dialkyl carbonate, which method
comprises reacting together carbon monoxide, oxygen, and alcohol in
the presence of a catalyst, which catalyst comprises (a) a copper
compound not containing halogen atoms, and (b) an acid halide.
9. The method for manufacturing dialkyl carbonate according to
claim 8, wherein the copper compound not containing halogen atoms
is at least one copper compound selected from the group consisting
of copper dimethoxide, copper diethoxide, copper dipropoxide,
cupric hydroxide (Cu(OH).sub.2), cupric nitrate
(Cu(NO.sub.3).sub.2), cupric acetate (Cu(OCOCH.sub.3).sub.2),
cupric sulfate (CuSO.sub.4), and basic copper carbonate
(CuCO.sub.3.multidot.Cu(OH).multidot.H.sub.2O).
10. The method for manufacturing dialkyl carbonate according to
claim 8, wherein the halide acid is hydrochloric acid.
11. The method for manufacturing dialkyl carbonate, which method
comprises reacting carbon monoxide, oxygen, and alcohol in the
presence of a catalyst, which catalyst is produced by combining
together ingredients comprising: (A) a copper compound not
containing halogen atoms, and (B) an alkoxide compound that can
react with the aforementioned (A) copper compound to produce a
copper alkoxide.
12. The method for manufacturing dialkyl carbonate according to
claim 11, wherein the copper compound not containing halogen atoms
is at least one copper compound selected from the group composed of
cupric hydroxide (Cu(OH).sub.2), cupric nitrate
(Cu(NO.sub.3).sub.2), cupric acetate (Cu(OCOCH.sub.3).sub.2),
cupric sulfate (CuSO.sub.4), basic copper carbonate
(CuCO.sub.3.multidot.Cu(OH).multidot.H.sub.2O), and cupric sulfate
(CuS).
13. The method for manufacturing dialkyl carbonate according to
claim 11, wherein the alkoxide compound capable of producing a
copper alkoxide is at least one compound selected from the group
composed of an alkali metal alkoxide, an alkaline earth metal
alkoxide, a quaternary ammonium alkoxide having formula (7) below,
R.sup.1R.sup.2R.sup.3R.sup.4NOR.sup.5 (7) and a quaternary
phosphonium alkoxide having formula (8) below;
R.sup.1R.sup.2R.sup.3R.sup.4POR.sup.5 (8) (wherein R.sup.1-R.sup.4
may be the same or different and denote hydrogen atoms or
hydrocarbon groups having 1-20 carbon atoms, and R.sup.5 denotes a
hydrocarbon group having 1-20 carbon atoms.
14. The method for manufacturing dialkyl carbonate according to
claim 11, wherein the alkoxide compound capable of producing a
copper alkoxide is used in an amount of 0.05-2.0 mol with respect
to the copper compound not containing halogen atoms.
15. The method for manufacturing dialkyl carbonate according to
claim 1, 5, 8 or 11 wherein the alcohol is methanol.
16. A method of making aromatic polycarbonate, which method
comprises reacting a dialkyl carbonate with a dihydroxy compound
where the dialkyl carbonate is made according to the method of
claim 1, 5, 8, or 11.
Description
[0001] The present application is a U.S. non-provisional
application based upon and claiming priority from Japanese
Application Nos. 2000-195029, 2000-195030, 2000-195031, and
2000-195032, with a filing date of Jun. 28, 2000 which are hereby
incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention concerns a method for manufacturing
dialkyl carbonate. More specifically, it concerns a method for
efficiently manufacturing dialkyl carbonate from CO, O.sub.2, and
alcohol.
BACKGROUND OF THE INVENTION
[0003] In recent years, aromatic polycarbonates have come to be
widely used in numerous fields as engineering plastics showing
outstanding mechanical properties such as impact resistance, as
well as outstanding heat resistance, transparency, etc.
[0004] The so-called phosgene method, in which aromatic dihydroxide
compounds such as bisphenol are reacted with phosgene by the
interfacial polycondensation method, has been widely used as a
method for manufacturing these aromatic polycarbonates. However,
the phosgene method currently in industrial use has been reported
to show many drawbacks, such as the fact that highly toxic phosgene
must be used, the fact that there are problems with processing the
large amounts of sodium hydroxide produced as a byproduct, and
health and pollution problems resulting from the methylene chloride
ordinarily used as a reaction solvent.
[0005] The process of transesterification (melting method) of
aromatic dihydroxy compounds and carbonic acid diesters using
alkali metal compounds such as sodium hydroxide as catalysts is
known as a method for manufacturing aromatic polycarbonates other
than the phosgene method. This method has attracted widespread
attention due to its advantage of allowing manufacturing using
inexpensive aromatic polycarbonates and the fact that it is
desirable from an environmental hygiene standpoint as it does not
require the use of toxic compounds such as phosgene and methylene
chloride.
[0006] In manufacturing polycarbonate using such melt methods,
diaryl carbonates such as diphenyl carbonate are used as carbonic
acid diesters. This diaryl carbonate, as disclosed in Japanese
Unexamined Patent Application Publication No. H9-194430, is
manufactured by transesterification of dialkyl carbonate and a
hydroxyl-group-containing aromatic hydrocarbon such as phenol. The
dialkyl carbonate used as a raw material for this diaryl carbonate
is manufactured from carbon monoxide, oxygen, and alcohol using a
catalyst composed of a cuprous halide such as cuprous chloride.
[0007] For example, when methanol is used as an alcohol, dimethyl
carbonate is manufactured by the following reaction:
2CH.sub.3OH+CO+1/2O.sub.2.fwdarw.(CH.sub.3O).sub.2CO+H.sub.2O
[0008] Concerning the cuprous chloride used as a catalyst in this
case, in a primary reaction, cupric methoxychloride is formed by
the reaction
2CuCl+2CH.sub.3OH+1/2O.sub.2.fwdarw.2Cu(OCH.sub.3)Cl+H.sub.2O
[0009] and it is thought that regeneration occurs in the following
secondary reaction:
2Cu(OCH.sub.3)Cl+CO.fwdarw.(CH.sub.3O).sub.2CO+2CuCl.
[0010] Moreover, the method of adding a hydroacid halide to the
reaction system in order to increase the catalytic activity of the
cuprous halide used as the catalyst has been presented (cf.
Japanese Unexamined Patent Application No. H5-194327).
[0011] However, in the above method in which a cuprous halide is
used as a catalyst, as the conversion rate of the aforementioned
cupric alkoxy chloride formed is low, the yield of the dialkyl
carbonate obtained may not be sufficient, and the catalyst used may
cause clogging of the reaction vessel and tubing, impairing
manufacturing efficiency.
SUMMARY OF THE INVENTION
[0012] Against this backdrop, the inventors of the present
invention conducted thorough studies on methods for efficiently
manufacturing dialkyl carbonate, and they discovered that by using
a combination of specified copper compounds and other metal
compounds as a catalyst, it is possible to produce dialkyl
carbonate in a high yield while maintaining high catalytic activity
during the reaction without clogging of the reaction vessel,
tubing, etc., by the catalyst, thus perfecting the present
invention.
[0013] The present invention was developed based on the above prior
art in order to provide a method for efficiently manufacturing
dialkyl carbonate from CO, O.sub.2, and alcohol.
[0014] The method for manufacturing dialkyl carbonate of the
present invention uses one of catalysts 1-5 below as a catalyst in
the manufacture of dialkyl carbonate using carbon monoxide, oxygen,
and alcohol as starting materials.
[0015] Catalyst 1: A catalyst prepared by mixing (i) a cupric
halide and (ii-1) an alkoxide compound of a metal from groups III
through VIII of the periodic table.
[0016] Catalyst 2: A catalyst prepared by mixing (i) a cupric
halide, (ii-2) a metal halide compound from groups III through VIII
of the periodic table, (ii-3) at least one compound selected from
the group composed of an alkali metal alkoxide, an alkaline earth
metal alkoxide, a quaternary ammonium alkoxide having Formula (1)
below, and a quaternary phosphonium alkoxide having Formula (2)
below, with it being possible to use a substance containing the
following:
R.sup.1R.sup.2R.sup.3R.sup.4NOR.sup.5 (1)
R.sup.1R.sup.2R.sup.3R.sup.4POR.sup.5 (2)
[0017] (where R.sup.1-R.sup.4 may be the same or different and
denote hydrogen atoms or hydrocarbon groups having 1-20 carbon
atoms, and R.sup.5 denotes a hydrocarbon group having 1-20 carbon
atoms.)
[0018] Catalyst 3: A catalyst prepared by mixing (I) a copper
halide and (II) an alkaline earth metal halide.
[0019] Catalyst 4: A catalyst prepared by mixing (a) a copper
compound not containing halogen atoms and (b) a halide acid.
[0020] Catalyst 5: A catalyst prepared by mixing (A) a copper
compound not containing halogen atoms and (B) an alkoxide compound
capable of being reacted with the aforementioned (A) copper
compound to produce a copper alkoxide.
[0021] The alcohol used in the manufacturing method for dialkyl
carbonate of the present invention should preferably be
methanol.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The following is a detailed description of the method for
manufacturing dialkyl carbonate of the present invention.
[0023] We will first explain the starting materials and catalysts
used in the method for manufacturing dialkyl carbonate of the
present invention.
[0024] Starting Materials and Catalysts
[0025] In the present invention, carbon monoxide (CO), oxygen
(O.sub.2), and alcohol are used as starting materials.
[0026] There are no particular restrictions on the alcohol used as
a starting material, with examples including methanol, ethanol,
propanol, butanol, isopropanol, isobutanol, and hexanol. Among
these, methanol should preferably be used.
[0027] Catalysts 1-5 below may be used as the catalyst of the
present invention.
[0028] Catalyst 1: A catalyst composed of (i) a cupric halide and
(ii-1) an alkoxide compound of a metal from groups III through VIII
of the periodic table.
[0029] Catalyst 2: A catalyst composed of (i) a cupric halide,
(ii-2) a metal halide compound from groups III through VIII of the
periodic table, (ii-3) at least one compound selected from the
group composed of an alkali metal alkoxide, an alkaline earth metal
alkoxide, a quaternary ammonium alkoxide having Formula (1) below,
and a quaternary phosphonium alkoxide having Formula (2) below,
with it being possible to use a substance containing the
following:
R.sup.1R.sup.2R.sup.3R.sup.4NOR.sup.5 (1)
R.sup.1R.sup.2R.sup.3R.sup.4POR.sup.5 (2)
[0030] (where R.sup.1-R.sup.4 may be the same or different and
denote hydrogen atoms or hydrocarbon groups having 1-20 carbon
atoms, and R.sup.5 denotes a hydrocarbon group having 1-20 carbon
atoms.)
[0031] Catalyst 3: A catalyst composed of (I) a copper halide and
(II) an alkaline earth metal halide.
[0032] Catalyst 4: A catalyst composed of (a) a copper compound not
containing halogen atoms and (b) a halide acid.
[0033] Catalyst 5: A catalyst composed of (A) a copper compound not
containing halogen atoms and (B) an alkoxide compound capable of
being reacted with the aforementioned (A) copper compound to
produce a copper alkoxide.
[0034] The various catalysts are explained below.
[0035] Catalysts 1 and 2
[0036] Examples of (i) the cupric halide used in catalyst 1 include
cupric chloride, cupric fluoride, cupric bromide, and cupric
iodide. These may also be used in mixtures of two or more. Among
these substances, cupric chloride is preferred.
[0037] An example of (ii-1) the alkoxide compound of a metal from
groups III through VIII of the periodic table is the alkoxide
compound shown in Formula (3) below.
M(OR.sup.a).sub.n (3)
[0038] (In Formula 1 [sic], M denotes a metal from groups III
through VIII of the periodic table, R.sup.a denotes a hydrocarbon
group having 1-20 carbon atoms, and n denotes the valence of
M.)
[0039] Examples of the metal from groups III through VIII of the
periodic table include metals such as aluminum, gallium, indium,
yttrium, thallium, silicon, germanium, titanium, tin, zirconium,
lead, hafnium, vanadium, antimony, niobium, tantalum, chromium,
tellurium, molybdenum, tungsten, iron, cobalt, nickel, ruthenium,
rhodium, palladium, and platinum. Examples of the hydrocarbon group
having 1-20 carbon atoms include alicyclic hydrocarbon groups and
aromatic hydrocarbon groups such as phenyl, tolyl, and naphthyl
groups, which may optionally contain linear alkyl groups such as
methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups,
branched alkyl groups such isopropyl and isobutyl groups, and
branched groups such as cyclopentyl, cyclohexyl, and
methylcyclohexyl groups.
[0040] These metal alkoxides from groups III through VIII of the
periodic table may be mixed in combinations of two or more. Among
these, metal alkoxides such as aluminum triethoxide, titanium
tetramethoxide, aluminum trimethoxide, iron trimethoxide, cobalt
dimethoxide, nickel dimethoxide, vanadium tetramethoxide, and tin
tetramethoxide are preferred.
[0041] In catalyst 2, instead of (ii-1) the metal alkoxide from
groups III through VIII of the periodic table, (ii-2) a metal
halide from groups III through VIII of the periodic table and
(ii-3) at least one compound selected from the group composed of an
alkali metal alkoxide or alkaline earth metal alkoxide of Formula
(4) [sic] below, a quaternary ammonium alkoxide of Formula 1 below,
or a quaternary phosphonium alkoxide of Formula (2) below may be
used.
A(OR.sup.b).sub.m (3)
R.sup.1R.sup.2R.sup.3R.sup.4NOR.sup.b (1)
R.sup.1R.sup.2R.sup.3R.sup.4POR.sup.b (2)
[0042] (In the formula, A denotes an alkali metal or alkaline earth
metal, R.sup.b denotes a hydrocarbon group having 1-20 carbon
atoms, and m denotes the valence of A. Furthermore, R.sup.1-R.sup.4
may be the same or different and are hydrogen atoms or hydrocarbon
groups having 1-20 carbon atoms, and examples of hydrocarbon groups
having 1-20 carbon atoms are substances identical to those shown in
the above examples.)
[0043] Preferred examples of the halide of a metal from groups III
through VIII of the periodic table include fluorides, chlorides,
bromides, and iodides of aluminum, gallium, indium, yttrium,
thallium, silicon, germanium, titanium, tin, zirconium, lead,
hafnium, vanadium, antimony, niobium, tantalum, chromium,
tellurium, molybdenum, tungsten, iron, cobalt, nickel, ruthenium,
rhodium, palladium, and platinum, with chlorides being preferred
and substances such as aluminum chloride and titanium tetrachloride
being particularly preferred.
[0044] These halides may be used either individually or in
combinations of two or more.
[0045] Specific examples of alkali metal alkoxides include sodium
methoxide, lithium methoxide, potassium methoxide, rubidium
methoxide, cesium methoxide, sodium ethoxide, lithium ethoxide,
potassium ethoxide, rubidium ethoxide, cesium ethoxide, sodium
propoxide, lithium propoxide, potassium propoxide, rubidium
propoxide, cesium propoxide, sodium butoxide, lithium butoxide,
potassium butoxide, rubidium butoxide, cesium butoxide, sodium
pentoxide, lithium pentoxide, potassium pentoxide, rubidium
pentoxide, cesium pentoxide, sodium hexoxide, lithium hexoxide,
potassium hexoxide, rubidium hexoxide, cesium hexoxide, sodium
heptoxide, lithium heptoxide, potassium heptoxide, rubidium
heptoxide, cesium heptoxide, sodium octoxide, lithium octoxide,
potassium octoxide, rubidium octoxide, cesium octoxide, sodium
phenoxide, lithium phenoxide, potassium phenoxide, rubidium
phenoxide, and cesium phenoxide.
[0046] Specific examples of alkaline earth metal alkoxides include
mono- and dialkoxide compounds such as methoxides, ethoxides,
propoxides, butoxides, pentoxides, hexoxides, heptoxides,
octoxides, and phenoxides of beryllium, magnesium, calcium,
strontium, and barium.
[0047] Specific examples of quaternary ammonium alkoxides include
alkoxide compounds such as tetramethyl ammonium, tetraethyl
ammonium, tetrapropyl ammonium, tetrabutyl ammonium, tetrapentyl
ammonium, and tetraheptyl ammonium methoxides and tetraoctyl
ammonium and tetraphenyl ammonium methoxides, ethoxides,
propoxides, butoxides, pentoxides, hectoxides, heptoxides,
octoxides, and phenoxides.
[0048] Specific examples of quaternary phosphonium alkoxides
include alkoxide compounds such as tetramethyl phosphonium,
tetraethyl phosphonium, tetrapropyl phosphonium, tetrabutyl
phosphonium, tetrapentyl phosphonium, and tetraheptyl phosphonium
methoxides and tetraoctyl phosphonium and tetraphenyl phosphonium
methoxides, ethoxides, propoxides, butoxides, pentoxides,
hectoxides, heptoxides, octoxides, and phenoxides.
[0049] These alkoxide compounds may be used individually or in
combinations of two or more.
[0050] The aforementioned (ii-2) halide of a metal from groups III
through VIII of the periodic table and (ii-3) at least one compound
selected from the group composed of alkali metal alkoxides,
alkaline earth metal alkoxides, quaternary ammonium alkoxides, and
quaternary phosphonium alkoxides are reacted as follows to produce
an alkoxide compound of a metal from groups III through VIII of the
periodic table.
[0051] {circle over (1)} In the case of an alkali metal, quaternary
ammonium, or quaternary phosphonium alkoxide:
MX.sub.n+nA.sup.1(OR.sup.b).fwdarw.M(OR.sup.b).sub.n+nA.sup.1X
[0052] {circle over (2)} In the case of an alkaline earth metal
alkoxide:
MX.sub.n+(n/2).multidot.A.sup.2(OR.sup.b).sub.2.fwdarw.M(OR.sup.b).sub.n+(-
n/2).multidot.A.sup.2X.sub.2n
[0053] (In the above reaction formulas, X denotes a halogen, M
denotes a metal from groups III through VIII of the periodic table,
and n denotes the valence of M. Moreover, A.sup.1 denotes an alkali
metal, quaternary ammonium, or quaternary phosphonium, A.sup.2
denotes an alkaline earth metal, and R.sup.b denotes a hydrocarbon
group having 1-20 carbon atoms.)
[0054] In the present invention, an alkoxide compound of a metal
from groups III through VIII of the periodic table obtained in the
above reactions may be used as catalyst 2; alternatively, (ii-2) a
metal halide from groups III through VIII of the periodic table
that is either unreacted or in the process of being reacted and
(ii-3) at least one compound selected from the group composed of an
alkali metal alkoxide or alkaline earth metal alkoxide having
Formula (2) above, a quaternary ammonium alkoxide having Formula
(3) above, and a quaternary phosphonium alkoxide having Formula (4)
[sic] above may also be used as catalyst 2.
[0055] The ratio of (ii-2) the metal halide from groups III through
VIII of the periodic table to (ii-3) the alkoxide compound selected
from the group composed of an alkali metal alkoxide, an alkaline
earth metal alkoxide, a quaternary ammonium alkoxide, and a
quaternary phosphonium alkoxide (alkoxy groups in alkoxide
compound/halogens in halide) should be a molar ratio in the range
of 0.5-2.0, and preferably 0.9-1.5.
[0056] In reacting the aforementioned alkoxide compound and the
aforementioned halide, the reaction should preferably be carried
out at a temperature of 0-120.degree. C. using R.sup.bOH as a
solvent. The reaction mixture composed of the alkoxide compound of
a metal from groups III through VIII of the periodic table obtained
and the alkali metal, alkaline earth metal, quaternary ammonium, or
quaternary phosphonium halide may be used as is, but the alkali
metal, alkaline earth metal, quaternary ammonium, or quaternary
ammonium halide (AX.sub.m) produced may also be removed by a
process such as filtration.
[0057] Catalyst 3
[0058] Examples of (I) the copper halide used as catalyst 3 include
cuprous chloride, cupric chloride, cuprous fluoride, cupric
fluoride, cuprous bromide, cupric bromide, cuprous iodide, and
cupric iodide. Of these substances, a monovalent copper compound is
preferred, with cuprous chloride being particularly well-suited
from the standpoint of activity.
[0059] Examples of (II) the alkali metal halide include magnesium
chloride, magnesium fluoride, magnesium bromide, magnesium iodide,
calcium chloride, calcium fluoride, calcium bromide, calcium
iodide, strontium chloride, strontium fluoride, strontium bromide,
strontium iodide, barium chloride, barium fluoride, barium bromide,
and barium iodide.
[0060] These copper halides and alkali metal halide compounds may
be used either individually or in mixtures of two or more. Among
these, magnesium chloride and barium chloride are particularly
preferred from the standpoint of activity.
[0061] Catalyst 4
[0062] Examples of the (a) copper compound not containing halogen
atoms used as catalyst 4 include the copper alkoxide compounds of
Formulas (4) and (5) below.
Cu(OR).sub.2 (4)
Cu(OR) (5)
[0063] In the formula, R denotes a hydrocarbon group having 1-20
carbon atoms. Examples of hydrocarbon groups having 1-20 carbon
atoms that may be used include alicyclic hydrocarbon groups that
may have linear alkyl groups such as methyl, ethyl, propyl, butyl,
pentyl, hexyl, and octyl groups, branched alkyl groups such as
isopropyl and isobutyl groups, or branched groups such as
cyclopentyl, cyclohexyl, or methylcyclohexyl groups and aromatic
hydrocarbon groups such as phenyl, tolyl, and naphthyl groups.
Examples of these copper alkoxide compounds that may be used
include copper dimethoxide, copper diethoxide, copper dipropoxide,
copper dibutoxide, copper diphenoxide, copper methoxide, copper
ethoxide, copper propoxide, copper butoxide, and copper phenoxide.
Moreover, copper chelate compounds such as copper acetylacetonate
chelate may also be used.
[0064] Furthermore, examples of copper compounds not containing
halogen atoms that may be used include inorganic copper compounds
such as cupric hydroxide (Cu(OH).sub.2), cupric nitrate
(Cu(NO.sub.3).sub.2), cupric acetate (Cu(OCOCH.sub.3).sub.2),
cupric oxalate, cupric phosphate, cupric phthalate, cupric formate,
cupric sulfate (CuSO.sub.4), basic cupric carbonate
(CuCO.sub.3.multidot.Cu(OH).multidot.H.sub.2O), cuprous hydroxide
(CuOH), cuprous nitrate (CuNO.sub.3), cuprous acetate
(CuOCOCH.sub.3), cuprous oxalate, cuprous phosphate, cuprous
phthalate, cuprous formate, and cuprous sulfate
(Cu.sub.2SO.sub.4).
[0065] Among these substances, divalent copper-containing compounds
are preferred, preferably at least one compound selected from the
group composed of copper dimethoxide, copper diethoxide, copper
dipropoxide, cupric hydroxide (Cu(OH).sub.2), cupric nitrate
(Cu(NO.sub.3).sub.2), cupric acetate (Cu(OCOCH.sub.3).sub.2),
cupric sulfate (CuSO.sub.4), and basic copper carbonate
(CuCO.sub.3.multidot.Cu(OH).multidot.H.sub.2O).
[0066] Two or more of these copper compounds not containing halogen
atoms may also be used in combination.
[0067] Examples of (b) halide acids include hydrogen halide (HX: X
denotes a halogen) acids such as hydrofluoric acid (HF),
hydrochloric acid (HCl), and bromic acid (HBr) Two or more halide
acids may also be used in combination.
[0068] Among these substances, hydrochloric acid is preferred in
the present invention from the standpoint of activity.
[0069] Catalyst 5
[0070] An example of (A) the copper compound not containing halogen
atoms used in catalyst 5 is the same compound used in the
aforementioned catalyst 4.
[0071] These copper compounds not containing halogen atoms may also
be used in combinations of two or more.
[0072] Moreover, as (B) the alkoxide compound that is reacted with
the aforementioned (A) copper compound to produce a copper
alkoxide, one should preferably use at least one compound selected
from the group composed of an alkali metal alkoxide, an alkaline
earth metal alkoxide, the quaternary ammonium alkoxide of Formula
(1) above, and the quaternary phosphonium alkoxide of Formula (2)
above.
[0073] Examples of the alkali metal alkoxide include an alkaline
earth metal alkoxide, a quaternary ammonium alkoxide, and a
quaternary phosphonium, the same as the substances mentioned above.
These alkoxide compounds may also be used in combinations of two or
more.
[0074] The aforementioned (A) copper compound not containing
halogen atoms and (B) the alkoxide compound capable of being
reacted with (A) the aforementioned copper compound to produce a
copper alkoxide are reacted to produce a copper alkoxide not
containing halogen atoms.
[0075] When the aforementioned catalysts 1-5 are used, catalytic
activity in manufacturing of dialkyl carbonate using carbon
monoxide, oxygen, and alcohol as starting materials is high and the
reaction is stable, making it possible to maintain catalytic
activity over long periods.
[0076] Manufacturing of Dialkyl Carbonate
[0077] In the present invention, the aforementioned catalysts 1-5
are used in manufacturing dialkyl carbonate using carbon monoxide,
oxygen, and alcohol as starting materials.
[0078] When catalyst 1 or 2 is used, one first takes (i) a cupric
halide and (ii-1) an alkoxide compound of a metal from groups III
through VIII of the periodic table, or (i) a cupric halide, (ii-2)
a metal halide from groups III through VIII of the periodic table,
and (ii-3) at least one compound selected from the group composed
of an alkali metal alkoxide, an alkaline earth metal alkoxide, the
quaternary ammonium alkoxide of Formula (1) above, and the
quaternary phosphonium alkoxide of Formula (2) above, adds them to
the alcohol used as a raw material, and carries out a reaction to
prepare raw material alcohol containing catalytic components.
[0079] The (i) cupric halide, (ii-1) metal alkoxide from groups III
through VIII of the periodic table, and cupric halide should be
added in the amount of 0.0011-1.0 mol, and preferably 0.005-0.2 mol
per mol of alcohol.
[0080] The (ii-1) alkoxide compound of a metal from groups III
through VIII of the periodic table should be added in the amount of
0.05-2.0 mol, and preferably 0.1-1.2 mol with respect to (i) the
cupric halide.
[0081] In the case of use of catalyst 2, when (ii-2) the metal
halide from groups III through VIII of the periodic table and
(ii-3) the alkoxide compound selected from the group composed of
the aforementioned alkali metal alkoxide, alkaline earth metal
alkoxide, quaternary ammonium alkoxide, and quaternary phosphonium
alkoxide are used as the catalyst, (ii-2) the metal halide from
groups III through VIII of the periodic table should be added in
the amount of 0.05-2.0 mol, and preferably 0.1-1 mol with respect
to (i) the cupric halide. Moreover, the (ii-3) alkoxide compound,
with respect to (ii-2) the metal halide from groups III through
VIII of the periodic table, should be added in a molar ratio
(alkoxy groups in (ii-3) the alkoxide compound/halogens in (ii-2)
the halogen compound) of 0.5-2.0, and preferably 0.9-1.5.
[0082] When catalyst 3 is used, specifically, one first adds the
catalyst composed of (I) the copper halide and (II) the alkali
metal halide to the raw material alcohol and then reacts it to
prepare raw material alcohol containing catalytic components.
[0083] (I) The copper halide should be added in the amount of
0.001-1.0 mol, and preferably 0.005-0.2 mol per mol of alcohol.
[0084] The catalyst composed of (II) an alkali metal halide should
be added with respect to (I) the copper halide in an alkaline earth
metal/copper atom ratio of 0.05-2.0 mol, and preferably 0.1-1.2
mol.
[0085] When catalyst 4 is used, specifically, one first adds the
catalyst composed of (a) the copper compound not containing halogen
atoms and (b) a halide acid to the raw material alcohol and reacts
the mixture in order to obtain raw material alcohol containing
catalytic components.
[0086] Moreover, the (a) copper compound not containing halogen
atoms should be added in the amount of 0.001-1.0 mol, and
preferably 0.005-2.0 mol per mol of alcohol.
[0087] The catalyst composed of (b) a halide acid should be added
with respect to (a) the copper compound not containing halogen
atoms with a ratio of Cl atoms in the halide acid to the copper
atoms in the copper compound (Cl/Cu) of 0.05-2.0 mol, and
preferably 0.1-1.2 mol.
[0088] When catalyst 5 is used, one first adds the catalyst
composed of (A) a copper compound not containing halogen atoms and
(B) an alkoxide compound capable of producing copper alkoxide when
reacted with (B) the aforementioned (A) copper compound to the raw
material alcohol and then carries out the reaction in order to
prepare raw-material alcohol containing catalytic components.
[0089] Furthermore, (A) the copper compound not containing halogen
atoms should be added in the amount of 0.001-1.0 mol, and
preferably 0.005-2.0 mol per mol of alcohol.
[0090] The aforementioned (A) copper compound and (B) alkoxide
compound capable of being reacted with said copper compound to
produce a copper alkoxide should be added in such a way that the
molar ratio of the alkoxy groups in (ii) the alkoxide compound
capable of being reacted with the aforementioned (i) copper
compound to produce a copper alkoxide with respect to the copper
atoms in (i) the copper compound not containing halogen atoms
(alkoxy groups/Cu) is 0.05-2.0 mol, and preferably 0.1-1.2 mol.
[0091] When catalysts 1, 2, 3, or 5 are used, one may also add a
hydroacid halide (halide acid) together with the catalyst.
[0092] Next, carbon monoxide and oxygen gas are introduced under
pressure into the alcohol containing catalytic components.
Moreover, the carbon monoxide and oxygen may be introduced into the
alcohol containing catalytic components individually, or they may
be premixed and introduced together. At this stage, gases that do
not generate the reaction product, specifically hydrogen, nitrogen,
carbon dioxide, methane, and inert gases such as argon, may be
present in the reaction system.
[0093] The amount of carbon monoxide introduced should preferably
be greater than the stoichiometric number. For this reason, the
molar ratio of the carbon dioxide to the oxygen introduced (carbon
dioxide/oxygen) should be within the range of 3/1-100/1, and
preferably 20/1-100/1.
[0094] The reaction is ordinarily carried out at a temperature of
50-200.degree. C., and preferably 100-150.degree. C., and a
pressure of atmospheric pressure to 150 atmospheres, with a
pressure of 10-100 atmospheres being preferred.
[0095] Dialkyl carbonate is produced by the above reaction.
[0096] By means of the present invention, the yield of dialkyl
carbonate obtained can be increased.
[0097] Moreover, the dialkyl carbonate produced can be recovered by
a separation method known in the art, such as distillation,
filtering, decanting, centrifugation, demixing, or permeation
membrane separation. These separation methods may also be used in
combinations of two or more.
[0098] Catalysts contained in the reaction solution of recovered
dialkyl carbonate and unreacted alcohol, etc., may be recovered and
reused.
[0099] This type of reaction may be carried out using a batch-tank
reaction vessel or a continuous reaction vessel. It is particularly
preferable to use a pressure-resistant vessel such as an
autoclave.
[0100] In the case of a continuous reaction vessel, the alcohol,
carbon monoxide, and oxygen are introduced into the solution of the
aforementioned alcohol containing catalytic components and reacted.
Next, the reaction solution containing the dialkyl carbonate
produced, water, and alcohol, the unreacted carbon monoxide, and
water vapor are removed, the dialkyl carbonate and water are
removed from the reaction solution, and the other components are
recycled into the reaction system.
[0101] The reaction solution into which alcohol, carbon monoxide,
oxygen, and if necessary, a hydroacid halide have been introduced
may also contain unrecovered dialkyl carbonate. The reaction
solution into which alcohol, carbon monoxide, oxygen, and if
necessary, a hydroacid halide have been supplied should have an
alcohol concentration of 30-80% by weight, and preferably 35-80% by
weight, and a water concentration of 1-10% by weight, and
preferably 2-7% by weight.
[0102] In the above method for manufacturing dialkyl carbonate of
the present invention, the aforementioned catalysts 1-5 are used as
catalysts; by using these catalysts, it becomes possible to
efficiently manufacture dialkyl carbonate while maintaining high
catalytic activity.
[0103] According to the method for manufacturing dialkyl carbonate
of the present invention, a combination of specified catalysts is
used, so that by means of these catalysts, it becomes possible to
efficiently manufacture dialkyl carbonate while maintaining a high
degree of catalytic activity without clogging of the tubing or
reaction vessel. Moreover, when diaryl carbonate manufactured using
dialkyl carbonate obtained in this manner as a raw material is used
in polycondensation of polycarbonate, it is possible to obtain
polycarbonate having a favorable color tone, and this type of
polycarbonate is better suited than general molding materials for
use in applications including construction materials such as
sheets, automobile headlight lenses, optical lenses for glasses,
etc., and optical recording materials, and it is particularly
well-suited for molded materials used in optical disks.
WORKING EXAMPLES
[0104] The following is a concrete explanation of the present
invention by means of working examples, but the invention is by no
means limited to these examples.
Working Example 1
[0105] 47.2 g of methanol, 6.96 g of cupric chloride, and 2.25 g of
aluminum triethoxide (Al(OC.sub.2H.sub.2H.sub.5).sub.3 (Al/Cu molar
ratio=0.27) was placed in a hastelloy autoclave with an internal
volume of 300 mL and sealed.
[0106] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=4.87%, N.sub.2=3.59%, CO=91.54%,
CO.sub.2=0.00%) was fed into the autoclave at the rate of 18.7
mL/min to a total pressure of 2.5-2.6 MPa, and the reaction was
carried out for 60 minutes.
[0107] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0108] Moreover, the methanol-dimethyl carbonate conversion rate
was 6.5 mol %, and the amount of dimethyl carbonate produced was
5.7 g.
Working Example 2
[0109] 47.5 g of methanol, 6.96 g of cupric chloride, and 4.21 g of
aluminum triethoxide (Al(OC.sub.2H.sub.5).sub.3 (Al/Cu molar
ratio=0.51) was placed in a hastelloy autoclave having an internal
volume of 300 mL and sealed.
[0110] Next, the autoclave was heated to 125.degree. C., the same
reaction gas as that used in Working Example 1 was fed into the
autoclave at the rate of 18.5 mL/min to a total pressure of 2.5-2.6
MPa, and the mixture was reacted 60 minutes.
[0111] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction mixture composition were
quantitatively analyzed by gas chromatography.
[0112] Moreover, the methanol-dimethyl carbonate conversion rate
was 6.6 mol %, and the amount of dimethyl carbonate produced was
4.17 g.
Working Example 3
[0113] 47.1 g of methanol, 6.98 g of cupric chloride and 2.52 g of
titanium trimethoxide (Ti(OCH.sub.3).sub.4) (Ti/Cu molar
ratio=0.29) was placed in a hastelloy autoclave having an internal
volume of 300 mL and sealed.
[0114] Next, the autoclave was heated to 125.degree. C., and the
same reaction gas as that used in Working Example 1 was fed into
the autoclave at a rate of 18.5 mL/min to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 60 minutes.
[0115] After the autoclave was cooled, the unreacted gas was slowly
removed, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0116] The methanol-dimethyl carbonate conversion rate was 6.1 mol
%, and the amount of dimethyl carbonate produced was 3.87 g.
Working Example 4
[0117] 48.3 g of methanol, 3.99 g of aluminum chloride (AlCl.sub.3)
(Al/Cu molar ratio=0.58) and 4.31 g of sodium methoxide
(NaOCH.sub.3) (molar ratio of (Cl in aluminum chloride/methoxy
groups in sodium methoxide)=1.12) was placed sequentially in a
hastelloy autoclave having an internal volume of 300 mL, after
which 6.98 g of cupric chloride was added and the autoclave was
sealed.
[0118] Next, the temperature of the autoclave was increased to
125.degree. C., the reaction gas (composition: O.sub.2=5.07%,
N.sub.2=6.15%, CO=88.80%, CO.sub.2=0.00%) was fed into the
autoclave at 20.0 mL/min to a total pressure of 2.5-2.6 MPa, and
the reaction was carried out for 60 minutes.
[0119] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0120] Moreover, the methanol-dimethyl carbonate conversion rate
was 5.5 mol %, and the amount of dimethyl carbonate produced was
3.54 g.
Working Example 5
[0121] 48.6 g of methanol, 5.53 g of cuprous chloride, and 1.04 mg
of magnesium chloride (MgCl.sub.2) (Mg/Cu molar ratio=0.195) was
placed in a hastelloy autoclave having an internal volume of 300
mL, and the autoclave was sealed.
[0122] Next, the autoclave was heated to 115.degree. C., the
reaction gas (composition: O.sub.2=4.31%, N.sub.2=1.57%, CO=93.83%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0123] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0124] Moreover, the methanol-dimethyl carbonate conversion rate
was 6.6 mol %, and the amount of dimethyl carbonate produced was
4.28 g.
Working Example 6
[0125] 46.9 g of methanol, 5.54 g of cuprous chloride, and 2.05 g
of magnesium chloride (MgCl.sub.2) (Mg/Cu molar ratio=0.384) was
placed in a hastelloy autoclave with an internal volume of 300
mL.
[0126] Next, the autoclave was heated to 115.degree. C., and the
reaction gas (composition: O.sub.2=4.78%, N.sub.2=0.32%, CO=94.90%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0127] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0128] Moreover, the methanol-dimethyl carbonate conversion rate
was 7.6 mol %, and the amount of dimethyl carbonate produced was
4.75 g.
Working Example 7
[0129] 48.4 g of methanol, 6.98 g of cupric chloride (CuCl.sub.2),
and 1.06 g of magnesium chloride (MgCl.sub.2) (Mg/Cu molar
ratio=0.214) was placed in a hastelloy autoclave having an internal
volume of 300 mL, and the autoclave was sealed.
[0130] Next, the autoclave was heated to 115.degree. C., the
reaction gas (composition: O.sub.2=4.31%, N.sub.2=1.57%, CO=93.83%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0131] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0132] Moreover, the methanol-dimethyl carbonate conversion rate
was 6.2 mol %, and the amount of dimethyl carbonate produced was
4.01 g.
Working Example 8
[0133] 47.0 g of methanol, 5.11 g of cuprous chloride, and 1.97 g
of calcium chloride (CaCl.sub.2) (Ca/Cu molar ratio=0.344) was
placed in a hastelloy autoclave having an internal volume of 300
mL, and the autoclave was sealed.
[0134] Next, the autoclave was heated to 115.degree. C., the
reaction gas (composition: O.sub.2=4.31%, N.sub.2=1.57%, CO=93.83%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0135] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0136] Moreover, the methanol-dimethyl carbonate conversion rate
was 7.8 mol %, and the amount of dimethyl carbonate produced was
4.88 g.
Working Example 9
[0137] 47.2 g of methanol, 5.07 g of cuprous chloride, and 4.14 g
of barium chloride (BaCl.sub.2 .multidot.2H.sub.2O) (Ba/Cu molar
ratio=0.336) was placed in a hastelloy autoclave having an internal
volume of 300 mL, and the autoclave was sealed.
[0138] Next, the autoclave was heated to 115.degree. C., the
reaction gas (composition: O.sub.2=4.31%, N.sub.2=1.57%, CO=93.83%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0139] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0140] Moreover, the methanol-dimethyl carbonate conversion rate
was 7.1 mol %, and the amount of dimethyl carbonate produced was
4.49 g.
Working Example 10
[0141] 47.3 g of methanol, 6.35 g of copper dimethoxide
(Cu(OCH.sub.3).sub.2), and 2.97 g of 36% hydrochloric acid (Cl/Cu
molar ratio=0.58) was placed in a hastelloy autoclave with an
internal volume of 300 mL, and the autoclave was sealed.
[0142] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=5.93%, N.sub.2=1.05%, CO=93.02%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0143] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0144] The resulting methanol-dimethyl carbonate conversion rate
was 5.4 mol %, and the amount of dimethyl carbonate produced was
3.44 g.
Working Example 11
[0145] 46.7 g of methanol, 6.20 g of copper dimethoxide
(Cu(OCH.sub.3).sub.2), and 4.21 g of 36% hydrochloric acid (Cl/Cu
molar ratio=0.84) was placed in a hastelloy autoclave with an
internal volume of 300 mL, and the autoclave was sealed.
[0146] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=4.63%, N.sub.2=4.67%, CO=90.70%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0147] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0148] The resulting methanol-dimethyl carbonate conversion rate
was 10.4 mol %, and the amount of dimethyl carbonate produced was
6.63 g.
Working Example 12
[0149] 47.6 g of methanol, 5.04 g of cupric hydroxide
(Cu(OH).sub.2), and 2.97 g of 36% hydrochloric acid (Cl/Cu molar
ratio=0.55) was placed in a hastelloy autoclave having an internal
volume of 300 mL, and the autoclave was sealed.
[0150] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=4.54%, N.sub.2=4.38%, CO=91.08%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0151] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0152] The resulting methanol-dimethyl carbonate conversion rate
was 5.5 mol %, and the amount of dimethyl carbonate produced was
3.51 g.
Working Example 13
[0153] 48.8 g of methanol, 9.29 g of cupric acetate
(Cu(OCOCH).sub.3).sub.2), and 5.11 g of 36% hydrochloric acid
(Cl/Cu molar ratio=0.99) was placed in a hastelloy autoclave with
an internal volume of 300 mL, and the autoclave was sealed.
[0154] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=5.08%, N.sub.2=2.53%, CO=92.39%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0155] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0156] The resulting methanol-dimethyl carbonate conversion rate
was 3.3 mol %, and the amount of dimethyl carbonate produced was
2.15 g.
Working Example 14
[0157] 47.3 g of methanol, 6.13 g of basic copper carbonate
(CuCO.sub.3.multidot.Cu(OH).multidot.H.sub.2O), and 5.00 g of 36%
hydrochloric acid (Cl/Cu molar ratio=0.96) was placed in a
hastelloy autoclave with an internal volume of 300 mL, and the
autoclave was sealed.
[0158] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=6.18%, N.sub.2=0.83%, CO=92.99%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0159] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0160] The resulting methanol-dimethyl carbonate conversion rate
was 9.0 mol %, and the amount of dimethyl carbonate produced was
5.70 g.
Working Example 15
[0161] 47.4 g of methanol, 9.27 g of cupric acetate, and 1.92 g of
sodium methoxide (NaOCH.sub.3/Cu (OCOCH.sub.3).sub.2 molar
ratio=0.7) was placed in a hastelloy autoclave with an internal
volume of 300 mL, and the autoclave was sealed.
[0162] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=4.16%, N.sub.2=1.52%, CO=94.32%,
CO.sub.2=0.00%) were fed into the autoclave at a rate of 27.0
mL/min to a total pressure of 2.5-2.6 MPa, and the reaction was
carried out for 60 minutes.
[0163] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0164] The resulting methanol-dimethyl carbonate conversion rate
was 2.9 mol %, and the amount of dimethyl carbonate produced was
1.84 g.
Working Example 16
[0165] 47.0 g of methanol, 5.06 g of cupric hydroxide
(Cu(OH).sub.2), and 1.36 g of sodium methoxide (NaOCH.sub.3/Cu
(OH).sub.2 molar ratio=0.48) was placed in a hastelloy autoclave
with an internal volume of 300 mL, and the autoclave was
sealed.
[0166] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=4.54%, N.sub.2=4.38%, CO=91.08%,
CO.sub.2=0.00%) was fed into the autoclave at a rate of 17.5 mL/min
to a total pressure of 2.5-2.6 MPa, and the reaction was carried
out for 60 minutes.
[0167] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0168] The resulting methanol-dimethyl carbonate conversion rate
was 3.4 mol %, and the amount of dimethyl carbonate produced was
2.16 g.
Working Example 17
[0169] 48.7 g of methanol, 4.97 g of cupric sulfate (CuS), and 2.07
g of sodium methoxide (NaOCH.sub.3/CuS molar ratio=0.74) was placed
in a hastelloy autoclave with an internal volume of 300 mL, and the
autoclave was sealed.
[0170] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=5.08%, N.sub.2=2.53%, CO=92.39%,
CO.sub.2=0.00%) was fed into the autoclave at a rate of 17.5 mL/min
to a total pressure of 2.5-2.6 MPa, and the reaction was carried
out for 60 minutes.
[0171] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0172] The resulting methanol-dimethyl carbonate conversion rate
was 3.7 mol %, and the amount of dimethyl carbonate produced was
2.38 g.
Working Example 18
[0173] 47.7 g of methanol, 9.20 g of cupric acetate, and 2.56 g of
potassium methoxide (KOCH.sub.3/Cu(OCOCH.sub.3).sub.2 molar
ratio=0.72) was placed in a hastelloy autoclave with an internal
volume of 300 mL, and the autoclave was sealed.
[0174] Next, the autoclave was heated to 125.degree. vC., and the
reaction gas (composition: O.sub.2=4.16%, N.sub.2=1.52%, CO=94.32%,
CO.sub.2=0.00%) was fed into the autoclave at a rate of 24.1 mL/min
to a total pressure of 2.5-2.6 MPa, and the reaction was carried
out for 60 minutes.
[0175] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0176] The resulting methanol-dimethyl carbonate conversion rate
was 2.5 mol %, and the amount of dimethyl carbonate produced was
1.61 g.
[0177] Moreover, in Working Examples 1-18, the production of
methylal as a byproduct was confirmed in all cases.
Comparison Example 1
[0178] 46.5 g of methanol and 6.92 g of cupric chloride was placed
in a hastelloy autoclave with an internal volume of 300 mL, and the
autoclave was sealed.
[0179] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=5.07%, N.sub.2=6.15%, CO=88.88%,
CO.sub.2=0.00%) was fed into the autoclave at a rate of 31.0 mL/min
to a total pressure of 2.5-2.6 MPa, and the reaction was carried
out for 60 minutes.
[0180] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0181] Moreover, the methanol-dimethyl carbonate conversion rate
was 5.0 mol %, and the amount of dimethyl carbonate produced was
3.14 g.
Comparison Example 2
[0182] 47.2 g of methanol and 5.43 g of cuprous chloride was placed
in a hastelloy autoclave with an internal volume of 300 mL, and the
autoclave was sealed.
[0183] Next, the autoclave was heated to 115.degree. C., the
reaction gas (composition: O.sub.2=4.40%, N.sub.2=0.54%, CO=95.03%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0184] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0185] Moreover, the methanol-dimethyl carbonate conversion rate
was 5.6 mol %, and the amount of dimethyl carbonate produced was
3.55 g.
Comparison Example 3
[0186] 47.1 g of methanol and 7.04 g of cupric chloride
(CuCl.sub.2) was placed in a hastelloy autoclave with an internal
volume of 300 mL, and the autoclave was sealed.
[0187] Next, the autoclave was heated to 115.degree. C., the
reaction gas (composition: O.sub.2=4.40%, N.sub.2=0.54%, CO=95.03%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0188] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0189] Moreover, the methanol-dimethyl carbonate conversion rate
was 5.4 mol %, and the amount of dimethyl carbonate produced was
3.37 g.
Comparison Example 4
[0190] 46.7 g of methanol and 6.20 g of copper dimethoxide
(Cu(OCH.sub.3).sub.2 was placed in a hastelloy autoclave with an
internal volume of 300 mL, and the autoclave was sealed.
[0191] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=5.93%, N.sub.2=1.05%, CO=93.02%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0192] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0193] The resulting methanol-dimethyl carbonate conversion rate
was 0.8 mol %, and the amount of dimethyl carbonate produced was
0.53 g.
[0194] The production of methylal as a byproduct was confirmed.
Comparison Example 5
[0195] 47.7 g of methanol and 5.04 g of cupric hydroxide
(Cu(OH).sub.2) was placed in a hastelloy autoclave with an internal
volume of 300 mL, and the autoclave was sealed.
[0196] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=5.08%, N.sub.2=8.44%, CO=85.88%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0197] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0198] The resulting methanol-dimethyl carbonate conversion rate
was 0.2 mol %, and the amount of dimethyl carbonate produced was
0.14 g.
[0199] The production of methylal as a byproduct was confirmed.
Comparison Example 6
[0200] 47.2 g of methanol and 9.23 g of cupric acetate
(Cu(OCOCH.sub.3).sub.2 was placed in a hastelloy autoclave with an
internal volume of 300 mL, and the autoclave was sealed.
[0201] Next, the autoclave was heated to 125.degree. C., and the
reaction gas (composition: O.sub.2=5.08%, N.sub.2=2.53%, CO=92.39%,
CO.sub.2=0.00%) was fed into the autoclave at a rate of 25.0 mL/min
to a total pressure of 2.5-2.6 MPa, and the reaction was carried
out for 60 minutes.
[0202] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0203] The resulting methanol-dimethyl carbonate conversion rate
was 0.7 mol %, and the amount of dimethyl carbonate produced was
0.47 g.
[0204] The production of methylal as a byproduct was confirmed.
Comparison Example 7
[0205] 47.7 g of methanol and 6.10 g of basic copper carbonate
(CuCO.sub.3 .multidot.Cu(OH).sub.2.multidot.H.sub.2O) was placed in
a hastelloy autoclave with an internal volume of 300 mL, and the
autoclave was sealed.
[0206] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=6.50%, N.sub.2=0.60%, CO=92.90%,
CO.sub.2=0.00%) was fed into the autoclave to a total pressure of
2.5-2.6 MPa, and the reaction was carried out for 30 minutes.
[0207] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0208] The resulting methanol-dimethyl carbonate conversion rate
was 0.1 mol %, and the amount of dimethyl carbonate produced was
0.08 g.
[0209] The production of methylal as a byproduct was confirmed.
Comparison Example 8
[0210] 47.2 g of methanol and 5.11 g of cupric hydrochloride
(Cu(OH).sub.2) was placed in a hastelloy autoclave with an internal
volume of 300 mL, and the autoclave was sealed.
[0211] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=5.08%, N.sub.2=8.44%, CO=85.88%,
CO.sub.2=0.00%) was fed into the autoclave at a rate of 27.0 mL/min
to a total pressure of 2.5-2.6 MPa, and the reaction was carried
out for 60 minutes.
[0212] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0213] The resulting methanol-dimethyl carbonate conversion rate
was 0.3 mol %, and the amount of dimethyl carbonate produced was
0.23 g.
[0214] The production of methylal as a byproduct was confirmed.
Comparison Example 9
[0215] 47.9 g of methanol and 4.91 g of cupric sulfate (CuS) was
placed in a hastelloy autoclave with an internal volume of 300 mL,
and the autoclave was sealed.
[0216] Next, the autoclave was heated to 125.degree. C., the
reaction gas (composition: O.sub.2=5.08%, N.sub.2=8.44%, CO=85.88%,
CO.sub.2=0.00%) was supplied to the autoclave at a rate of 21.5
mL/min to a total pressure of 2.5-2.6 MPa, and the reaction was
carried out for 60 minutes.
[0217] After the autoclave was cooled, the unreacted gas was slowly
purged, the reaction solution was removed, and the post-reaction
gas composition and reaction solution composition were
quantitatively analyzed by gas chromatography.
[0218] The resulting methanol-dimethyl carbonate conversion rate
was 0.2 mol %, and the amount of dimethyl carbonate produced was
0.11 g.
[0219] The production of methylal as a byproduct was confirmed.
* * * * *