JPH0196149A - Production of glycol esters - Google Patents

Abstract

PURPOSE:To obtain the titled substances in high yield, by reacting propylene with a lower aliphatic carboxylic acid and oxygen in the presence of a catalyst system consisting of a Pd component, alkaline (earth) metal component, halogen component, N-containing oxide component and specific metallic compound. CONSTITUTION:Propylene is reacted with a lower aliphatic carboxylic acid and oxygen to provide the titled substance. In the process, a system consisting of a Pd component (preferably metallic Pd), alkaline (earth) metal component (preferably LiCl or LiNO3), halogen component (preferably chloride ion), N- containing oxide component (especially nitric acid, etc.) and a specific metallic compound is used as a catalyst to stably and efficiently afford the aimed substances with high selectivity. Halides, nitrates, acetates, etc., of metals selected from group III, IV, V and VI elements and Fe, Ni, Rh, Mn, Cu and Co are preferably used as the metallic compound.

Description

[Detailed Description of the Invention] [Industrial Application Field] This book: 52i IJJ relates to a method for producing glycol esters, more specifically, intermediates and solvents for chemicals.

Alternatively, the present invention relates to a production method capable of stably and efficiently obtaining glycol esters useful as raw materials for producing polymers, etc., with high selectivity and yield.

[Prior art and its problems] Conventionally, as a method for obtaining glycol esters by reacting olefin with oxygen and carboxylic acid in the presence of a catalyst, A method for producing ethylene glycol monoester by reacting ethylene and oxygen in an organic acid solution containing equimolar or more of an alkali or alkaline earth metal organic acid at a temperature below 80°C (Japanese Patent Publication No. 45-1
4773), ■ palladium or palladium salt,
Nitrogen-containing oxide and halogen/palladium atomic ratio of 0.5 to 5! A method for producing glycol esters by reacting internal olefins and oxygen in a carboxylic acid mixed solution containing an amount of an alkaline earth halide (Japanese Patent Application Laid-open No. 14773/1983), ■ Palladium catalyst and An unsaturated compound and oxygen are introduced into a lower fatty acid carboxylic acid in the presence of an oxygen nitrogen compound and then reacted.

A method of producing glycol esters by stopping the introduction of the unsaturated compound and oxygen, introducing hydrogen to reduce the palladium catalyst, then separating the product, and subjecting the obtained residue to the reaction again. (Unexamined Japanese Patent Publication No. 58-177936
Publication No.) etc. are known.

However, these methods have problems in that glycol esters cannot be obtained in high yield or high selectivity, or that the catalyst is likely to be deactivated or the selectivity may be reduced. in particular.

If a catalyst is used in which the molar ratio (NOx/Pd) of the nitrogen-containing oxide component to the palladium component is 5 or more, the palladium component will be severely deactivated.
In addition, the molar ratio of the halogen component to the palladium component is C
When using a catalyst with CI /Pd) of 5 or more,
The olefin conversion rate decreases, and the molar ratio of nitrogen-containing oxide components and halogen components is relatively low (NOx/C
If the reaction was continued using a catalyst system in which the range of Pd)=(0,1-5)/(1-5)/1 was used, there was a drawback that the selectivity gradually decreased.

The present invention has been made based on the above-mentioned circumstances, and its purpose is to solve the above-mentioned problems and to produce propylene glycol esters in high yield from propylene, oxygen, and lower aliphatic carboxylic acids. It is an object of the present invention to provide a process for producing glycol esters which is extremely advantageous in practice and can be obtained stably and efficiently with high selectivity and substantially no deactivation of the catalyst or decrease in selectivity.

[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted extensive research and found that palladium, alkali or alkaline earth gold (Ha), halogen components, nitrogen-containing oxides, etc. The inventors have discovered that the above object can be easily achieved by using a specific catalyst system containing a specific metal compound, and based on this knowledge, the present invention has been completed.

That is, the present invention relates to the production of glycol esters by reacting propylene, lower aliphatic carboxylic acids, and oxygen in the presence of a catalyst.

The catalyst comprises (A) a palladium component, (B) an alkali metal component and/or an alkaline earth metal component, (C) a halogen component, (D) a nitrogen-containing oxide component, and (E) an element of Group I of the periodic table. Group IV elements, Group V elements, Group II elements, as well as Fe, Ni, Ru, Mn, Cu and G.

The present invention provides a method for producing glycol esters characterized by containing one or more metal compounds selected from the following.

The present invention will be explained in detail below.

-Reaction raw material and solvent- In the present invention, propylene used as a reaction raw material is
Pure ones or those containing impurities such as moisture, air, saturated hydrocarbons, and other olefins can be used as long as they do not interfere with the purpose of the present invention. most 1
In the present invention.

Usually, industrial propylene of various purity produced by cracking naphtha can be suitably used, but propylene produced from other carbon resources such as natural gas or coal may also be used. .

Oxygen used as a reaction raw material (oxidizing agent) can be used as it is, but it can also be mixed with an inert gas such as nitrogen.Normally, air or oxygen-enriched air is used. or nitrogen-enriched air can be suitably used. The inert gas is not particularly limited as long as it does not interfere with the purpose of the present invention, and in addition to nitrogen, examples include saturated hydrocarbons such as methane, ethane, and propane, carbon dioxide, argon, and helium. etc., or a mixture thereof.

As for the ratio of oxygen and propylene used in the reaction, that is, the charging ratio, the molar ratio of (propylene 102) is usually 1.0 to 3.0, preferably.

1.6-2.2. Particularly preferably, it is within the range of 1.8 to 2.0. If this molar ratio is too large, the conversion rate of propylene may be insufficient or the deterioration of the catalyst may be accelerated, while if it is too small, it may fall into the explosive range. The explosive range for a mixture of propylene and air is 1 atm.

It is known that the propylene concentration is usually 2.1 to 53.0%.

The lower aliphatic carboxylic acid has the following general formula (I):
.

RICOOH (I) (In Formula 1, R1 represents an alkyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and these alkyl groups may be 5! or 5!, as long as they do not impede the purpose of the present invention. There is no particular restriction as long as it is represented by ) and can maintain a liquid state or solution state in the reaction system.

Specifically, for example, acetic acid, propionic acid, acetic acid, isoacetic acid, -9・Taimasa, isoS methane, hexanoic acid, isohexanoic acid, octanoic acid, isooctanoic acid, decanoic acid, palmitic acid, etc. Acetic acid is particularly suitable in terms of width.

These lower aliphatic carboxylic acids are usually used alone, but 2M or more may be used in combination.

In addition, these lower aliphatic carboxylic acids are 1 of the reaction raw materials.
However, it can also be used as a solvent for the reaction system during normal operation.

That is, in the method of the present invention, the solvent for the reaction system is usually the same type as the lower aliphatic carbon aliphatic, preferably the lower aliphatic carbon aliphatic used as the reaction raw material. However, if desired, these can be diluted with inert solvents such as saturated hydrocarbons, aromatic hydrocarbons, ethers, alcohols, and esters, and solvents that do not interfere with the reaction such as aromatic carboxylic acids. It is 8.

The lower aliphatic carboxylic acid is usually used in an amount equal to or more than the total amount of propylene used in the reaction, preferably.

It is desirable to use 1.0 to 20 times the amount by mole.

If this usage ratio is too small, the yield of glycol esters based on the propylene used may be low, or the catalyst activity and selectivity may be significantly reduced.

Catalyst - The catalyst used in the method of the present invention includes (A) a palladium component, (B) an alkali metal component or an alkaline earth metal component, (C) a halogen component, (D) a nitrogen-containing compound component, and a cocatalyst. Ingredients include (E) Group ■ elements, Group IV elements, Group V elements, Group ■ elements of the periodic table, as well as Fe, Xi, and R.
Contains a compound of one or more metals selected from the group consisting of U, Mn, Cu, and Curl.

Preparation for obtaining (A) palladium component of this catalyst! As the raw material, metal palladium, organic palladium compounds, inorganic palladium compounds, or mixtures thereof can be used, but usually, for example, powdered or fine particulate metal palladium, palladium black, palladium oxide, hydroxide, etc. Palladium or palladium salts such as palladium nitrate: palladium halides such as palladium chloride, palladium bromide, and palladium iodide, inorganic acid salts such as palladium nitrate, and organic acid salts such as palladium acetate can be suitably used. Among these, metal palladium, palladium chloride, palladium acetate, etc. are preferable, and metal palladium etc. are particularly preferable.

As mentioned above, these may be used alone or in combination of two or more.

Examples of the alkali metal component and alkaline earth metal of component (B) include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium,
Calcium, strontium, barium, etc. can be mentioned, and among them, lithium, sodium, potassium, etc. are preferable.

Particularly suitable is lithium.

J of these alkali metal components and alkaline earth metal components
There are no particular restrictions on the form of the raw material, and various compounds can be used, but usually halides such as chlorides, bromides, and iodides, nitrates,
It is preferable to use it as an oxygen acid salt such as nitrite or acetate.

In particular, it is suitable to use it as a chloride, nitrate, or the like.

Specifically, the forms of raw materials for preparing these alkali metal components and alkaline earth metal components include, for example, L
iF, LiC1, Liar, LiI, NaF, N
aC1, NaBr, Mar, KH, K(4, KBr
, K.I.

CsC1, CsBr, '14gcl2, Mg
Brz, Hgh, CaC12, SrC; l2, B
aC1? , LiNO3, Nano 3゜KNO3, C
5N(h, Mg(N(h)?, Ca(NO3)2.0
r(NO3)? , LiNO2, NaNO2, KNO2,
Examples include lithium acetate, sodium acetate, potassium acetate, cesium acetate, and magnesium acetate, among which Li(4, LiN0z, etc.) can be preferably used.

Note that these may be used alone or in combination of two or more.

Further, either the alkali metal component or the alkaline earth metal component may be used alone, or the alkali metal component and the alkaline earth metal component may be used simultaneously.

Examples of the halogen component (C) include fluoride ions, chloride ions, bromide ions, and iodide ions, and among them, chloride ions are preferred.

These halogen components are simple, namely C1y, B
r2 and I2. Hydrogen halide, i.e. HF, H
d, HBr and HI or various metal compounds.

For example, the palladium halide which is the component (A), such as PdG2, PdBr2. Pd12,
H7Pd (JL4, etc.) can be supplied as an alkali metal and/or alkaline earth metal halide which is the above-mentioned (B) component, various metal halides as a raw material for preparing the (E) component shown below, etc. can.

Among these, halides as raw materials for preparing the components (A) and (B) such as PdC12 and Lieu, and FeC13, NNC12, LaC03, Zr
CfL s, '; ncl s, GaC13, Nb
C1s, NnC12゜CrC13, C0C31, Ca
Preparation of (7) (E) component such as C12 Various halides as MN can be used as suitable preparation raw materials.

Note that these halogen components and raw materials for their preparation may be used singly or in combination of two or more.

The nitrogen-containing compound component of the component (b) is NOx, that is, No, NOz, N20:l, NO2, N2's,
N2O5; NO3 - that is, nitric acid 1 fuming nitric acid, nitrate; NOz - that is, nitrous acid, nitrite: nitrite ester, etc., and among these, nitric acid, nitrate, nitrite ester, etc. are suitable.

Salts of various metals can be used as these nitrates and nitrites, but usually, for example, Pd(NOx)2. LiNO3, NaNO3, KNO3
, Mg(NO3)2, Ca(NO3)2. LiNO2,
The above-mentioned examples (A) and (such as NaNO2, KNO2)
Metal nitrates and nitrites as component B), metal nitrates and nitrites as component (E) as exemplified below, or metal nitrates and nitrites as component (E) as exemplified below, etc. You can use it. Further, as the nitrite ester, various alkyl nitrites such as methyl nitrite, ethyl nitrite, propyl nitrite, and butyl nitrite can be suitably used. Among these:

LiNO3, Fe(NO3)2, etc. are suitable.

Note that these nitrogen-containing oxide components or raw materials for their preparation may be used alone or in combination of two or more.

Specific examples of the metal type of the metal compound of component (E) include Sc, Y, La, Ce, Pr.
, Nd.

Pa, Ss, Eu, Gd, Yb, Dy
, Ha, Er, T+w, Yb, L
u.

Ac, Th, ■, B, A! L, Ga
, In, Ti, Zr, Hf,
Si, Ge, Sn, Pb, Sb, Bi, c
r, No, W, S, Se.

Examples include Te, Fe, old, Ru, Nn, Cu, Go, among others, La, Zr, V
, Wb, Ga, Cr, Go, Fe, Ni,
Nn, Si, Ge, Sn, Gu, Te and Ru are preferred. There are no particular restrictions on the form of these metal compounds, and both inorganic compounds such as inorganic salts and organic metal compounds can be used as preparation materials, but halides, oxides, and water are usually used. Compounds that can be used as Lewis acids, such as oxides or hydrous oxides or oxoacid halides, inorganic acid salts such as nitrates, nitrites, and sulfates, and organic acid salts such as acetates, are preferably used. Inorganic acid salts such as halides, nitrates, acetates, etc. are suitable.

Specifically, for example, SCC Mi 3, YC Sen 3, L
aC13, CeC13, CeC1s,';mcl
3, TI C13, UCC20BCl3, AIC
l 3. GaC13, l11 (: 3゜Ticl a
, ZrC14, HfC1a, 5i(41s
, GeCls , 5nC12, 5nC14, 5bC1
5, B1C13, C; rcl 3°NoCJl 4,
MoCJl b, Idols, WCI b
, 5eCJly, TeC12, FeC12, FeC1
3, NrCl z, , Ru1ns.

NnG12, CuC12, CoC12, CoC13,
La1r3, ZrBr4. SnBr4, GaBr3.
NiBr2, FeBr3. MnBr2, FeI3
, NiI2, M11 Summer 2, 16 (NO3h, Ge
(NO3)3, Th(NO+)4. Ai (NO3)
3.Ga(NOx):+,Zr(N(h)2゜ZrC1
2, ZrC12(NOz)z, S+(NO3)2.5
n(NO3)4, Bi(N(h)3.0r(NO3h,
MoCJL a, WOCI s.

Fe(NO3)z, Fe(NOx)3. Old (N(h)
2. RLI (NO3) 3. Mn (N03)? , Cu(
NO3) 2, Go (803) 2. Go (NO3)
3, LaC0COCH5)z, CeC0COCH5
)3, An(OCOCHx):+, TJl(O
COCH3)4, Cr(OCOCH3h, N1(
OCOCH3)? , Ru(OCOCHz)3. Mn
(OCOCIB)? , Cu (OCOClhh, G
o(OCOCH3)2, Ru(OH)a,
H2TeOs, 5nCOH) 2.5n02・nH
2O, Cr2O3・nH2O, GO(OH)2. Ga2
O: +・nH2O.

Fe(OH)2. Fe2O3・nH2O,Xl(O
H)2. Cu(OH)2, La2O3・nH2
O, Zr(12-2H20, Nb705・nH2O, M
n(OH)2, among others, LaG 3. ZrC 4.5nCl 4 , Ga
C13, NbC1a, HnCl2, COCl2
, NiC12, RuC13, CuC12, CrC13,
FeC13, Fe(NO3)3, La(NO3)3, C
o(NO3)z, Xl(NO3)2. S+(NO3)z
, Cr(N(:h)3゜M!I(NO3)2, Gu(
NOx)2. La(OCOCH3)z, Gu(OCOC
Hz)3. Xl(OCOCH3)z, Cu(OCO
CH3)2゜Mu(OCOCH3)2. Go (OCO
CH3)2. Ru(OB)n, H2TeOs, etc. can be suitably used.

In addition, these can be used as an anhydride or a hydrate, and may be used alone or in combination of two or more types.

The proportion of the components (A) to (E) used in the catalyst used in the method of the present invention is usually 1.

It is desirable to set it within the following range.

The ratio of the component (B), that is, the alkali metal and alkaline earth metal components, is such that the molar ratio of (total amount of alkali metal atoms and alkaline earth metal atoms)/total palladium atoms is usually 1 to 15.0. It is preferably within the range of 1.0 to 10.0.

If this molar ratio is too large, the conversion rate of propylene may decrease; on the other hand, if it is too small, it becomes difficult to form an effective catalyst system, and the conversion rate may also decrease.

The above (C) ji component, that is, the usage ratio of the halogen component is such that the molar ratio of all halogen atoms/all palladium atoms is usually 0.1-15.0, preferably 0.2-5. O2 is particularly preferably within the range of 1.0 to 5.0.

If this molar ratio is less than 0.1, the solubility of palladium used may decrease, making it difficult to form an effective catalyst system, while if it exceeds 15.0, the conversion rate of probyle will decrease. Sometimes.

Use of the component (D), that is, a nitrogen-containing, oxygenated component;
1, the molar ratio of all nitrogen-containing oxide components/all palladium atoms is usually 0.1-15.0, preferably 0.2-5.
0, particularly preferably within the range of 0.5 to 5.0.

If this molar ratio is less than 0.1, the solubility of palladium may decrease and it may become difficult to form an effective catalyst system, while if it exceeds 15.0, the deactivation of palladium will increase. Sometimes.

The ratio of the metal compound used as component (E) is such that the molar ratio of the total amount of gold m atoms in component (E)/total palladium atoms is 0.
．． 1-20.0. Preferably, it is set within the range of 1.0 to 10.0.

If this molar ratio is less than 0.1, the yield and selectivity of the target product glycol ester may be insufficiently improved, or the reduction in catalyst activity and selectivity over time may be insufficiently suppressed. On the other hand, if it exceeds 20.0, the productivity per total amount of catalyst used will decrease, and in some cases, the catalyst activity and selectivity may actually decrease.

The amount of catalyst used in the reaction system is such that the weight concentration of all palladium atoms used in the solvent used is usually 0.001.
It is set within the range of ~10% by weight, preferably 0.001~5% by weight.

If this palladium concentration is too low, the productivity of the target product, especially the productivity per unit volume of the reactor, will be extremely low. On the other hand, if it is too high, the solubility of palladium will decrease, making it difficult to form an effective catalyst system. is difficult to form, resulting in lower selectivity and lower productivity per palladium catalyst used.

In the method of the present invention, the catalyst system containing the components (A) to (E) is uniformly dispersed in the lower aliphatic carboxylic acid or a mixed solvent of the lower aliphatic carboxylic acid and another inert solvent. forming a catalyst system, a partially homogeneous catalyst system, or a heterogeneous catalyst system, and adding to the solution or suspension system,
Propylene or a mixed gas containing propylene and an oxygen-containing inert gas such as oxygen or air, or a mixture thereof, are brought into contact by introducing or supplying them to the predetermined propylene/# elementary ratio. 1 reaction to produce propylene glycol esters.

As for this reaction condition, the reaction temperature is usually 20 to 120℃.
℃, preferably in the range of 20 to 80℃, and the reaction pressure is usually in the range of normal pressure to 10 kg/cm2G, preferably normal pressure to 5 kg/cm2G.

If the reaction temperature is too low, the reaction rate may be insufficient, while if it is too high, the selectivity will decrease. Also 1
If the reaction pressure is less than normal pressure, the reaction operation will be complicated,
Productivity may decrease, while if it is too high, selectivity may decrease.

The reaction time depends on the type of catalyst used, the composition of the reaction system,
Since it varies depending on other conditions such as reaction temperature, it cannot be specified as -, but the contact time is usually 0.001 to 1.
2.0 (g pd-hr/number of moles of propylene), preferably 0.005 to 1.1. (g pd-hr
/number of moles of propylene) is suitable.

The reaction method is not particularly limited, and any of a batch method, a semi-continuous method, and a continuous method can be used.

The state of the reaction system f6 may be either a liquid phase or a mixed state of gas and liquid phases such as a trickle bed. It is desirable to stir thoroughly.

As described above, the state of the catalyst in the reaction solution can be either homogeneous, heterogeneous, or a mixture thereof, but it is preferable to use it in a homogeneous state.

In addition, when carrying out the reaction, in addition to the gas containing the reaction raw materials, if desired, the above-mentioned inert gas may be separately introduced or supplied as a diluting gas.

In the manner described above, the target product, propylene glycols, can be obtained in high yield and with high selectivity.

The resulting glycol esters have the following general formula [wherein 1172 and R3 are usually each RiG]
O- (however, R1 represents the same group as R1 in the above general formula (I)) or a water atom (however, R2 and R
3 is excluding those in which both are hydrogen atoms. However, as a diluting solvent, a carboxylic acid other than the carboxylic acid represented by the general formula (I) or its esters is used as a diluting solvent. When used in a system or when a carboxylic acid salt other than the carboxylic acid represented by general formula (I) is used as a catalyst component, a portion of R2 and/or R3 may be replaced by the ester or other carboxylate used. It may also be an acyl group other than R 100- derived from an acid or a catalyst component. ] Represented by

In addition, in this reaction, by-products such as ketones, aldehydes, and alkylidene dicarboxylic acids are usually produced, although the amount thereof is small.

These glycols, esters, and by-products can be easily separated from the solvent and spent catalyst and purified by known separation and purification methods such as distillation and extraction.

Similarly, the solvent used was determined by known separation methods such as distillation number extraction.
The recovered solvent, which can be separated and purified depending on the purification method and recovered, can be used as it is or, if desired, after being further subjected to an appropriate purification operation, for use in the green recycling reaction system.

The product or the catalyst solution or catalyst from which the product and the solvent have been distilled off can be used repeatedly in the reaction system as is, or after suitably adjusting its composition as desired.

Further, unreacted propylene can be subjected to the reaction again as it is, or after readjusting the purity and mixture composition as desired.

The target product glycol esters that have been separated and purified can be used as they are or, if desired, re-prepared to an appropriate purity and suitably used as raw materials for various chemical intermediates and polymers, or as solvents. .

Furthermore, the separated and purified by-products can be used in various fields of application as they are, or if desired, after being re-prepared to an appropriate purity.

[Example] (Example 1) 2 equipped with a gas introduction pipe, thermometer, reflux pipe and stirring bar
00tJL Metal palladium (2,01
mmol), LiC1 (6,00 mmol), LiNo
3 (2.02 mmol), Fe(NO3)z9H20(
2.04 mmol) and acetic acid (120 ml), and
A homogeneous palladium body solution was prepared at 0°C.

A mixed gas of propylene (25 m/win, ) and # element (13 m/in, ) was introduced into the solution, and the mixture was heated to 60°C.
The reaction was carried out for 2 hours. The product was quantified by gas chromatography after cooling the reaction solution. The results are shown in Table 1.

(Examples 2 to 15) Instead of Fe(NO3) 39H20(7) in Example 1, Fe 3 (2.18 mmol),
Go(OAc)24H20 (2.10 mmol),
Gu(OAc)2(2, (15 mmol).

N1(OAch4H20 (2.02 mmol),
N1CR2 (2,02 mmol), I, acl 3 (
2,10 mmol), ZrC1a (1,91 mmol), H2Te03 (2,03 mmol), Ru(O
H) 4 (2,02 mmol), 5 ucl 4 (2,
02 mmol], acl 3 (2, (15 mmol), NbC14 (2,03 mmol), H
nCl 24H20 (2,10 mmol), O and Cr
The reaction was carried out in the same manner as in Example 1 except that (OAc)3 (2.02 mmol) was used. The results are shown in Table 1.

(Comparative Example 1) The reaction was carried out in the same manner as in Example 1 except that FeCN03)39H20 was not used in Example 1. The results are shown in Table 1.

Table 1 Example I Fe(NO3)39H2O97,0//
2 FeCl3 96.8tt 3 Go(
OAc)24H2096,6tt4Cu(OAc
)2 97.2tt 5 Xl(OAc)24H
2096,2tt 5 Ni0 sentence 2 95.8t
t 7 La (i3 95.4// 8 Zr
C1a 93.0 // 9 H2Te02
96.5tt 10 Ru(OH)4 96.
0// 11 5uC1495-O tt 12 GaCl394.5 t/ 13 NbCl5 93.7// 14
0r(OAc)3 95.9// 15 MnC
l295.6 Comparative example! 90.8PGM
A nib oL: +z)g')ko-hE)? Set
Ac=OCOCH3PGDA nib a bilene glycol di-1 acetate [Effects of the invention] According to the invention, a specific catalyst system, especially a catalyst system in which a specific metal compound is added as a co-catalyst, is used, so propylene and oxygen and a lower aliphatic carboxylic acid,
Practically advantageous glycol esters that can be efficiently obtained from propylene glycols in high yield and high selectivity through stable operations that significantly suppress the decline in catalyst activity selectivity over time. A manufacturing method can be provided.

Claims (3)

[Claims] (1) When producing glycol esters by reacting propylene, a lower aliphatic carboxylic acid, and oxygen in the presence of a catalyst, the catalyst may contain (A) a palladium component,
(B) Alkali metal component and/or alkaline earth metal component, (C) Halogen component, (D) Nitrogen-containing oxide component, and (E) Group III element, Group IV element, Group V element, Group VI element of the periodic table. A method for producing glycol esters, comprising an element and a compound of one or more metals selected from Fe, Ni, Ru, Mn, Cu, and Co. (2) The method for producing glycol esters according to claim 1, wherein the metal compound as the component (E) is an inorganic compound of the metal. (3) The method for producing glycol esters according to claim 1, wherein the metal compound as the component (E) is an inorganic salt of the metal.