TW499421B - Process for preparing hydrogenated esters, the hydrogenation catalyst used, and process for preparing the catalyst - Google Patents

Abstract

A process for obtaining hydrogenated esters with high selectivity by the hydrogenation of an ester containing an unsaturated group of specific structure. Preferably, the hydrogenation reaction is conducted under the condition that the ester containing an unsaturated ester as material is diluted with an inert solvent and/or the concentration of carboxylic acid contained in the material is less than 1 wt.%. Preferably, the catalyst used in the above hydrogenation contains at least one metal selected from the elements of groups 8, 9 and 10 of the periodic table and has acid point of less than 1.0x10<SP>-1</SP> mmol/g.

Description

499421 A7 B7__ 5. Description of the invention (^ The present invention relates to a method for producing hydrogenated esters based on hydrogenation of unsaturated esters containing unsaturated groups. The hydrogenation catalyst that can be used in this method, K and the method for producing the catalyst. More details In other words, the present invention relates to reducing the amount of carboxylic acid produced by using hydrogenation catalyst to hydrogenate an unsaturated group-containing ester to obtain a corresponding hydrogenated ester. In addition, a method for producing a hydrogenated ester of an unsaturated ester of a raw material with a high conversion rate and a high selectivity (yield) into a hydrogenated ester of a product. The hydrogenation catalyst that can be used in this method, K and the catalyst The "(equivalent) hydrogenated ester" in this specification refers to the product obtained by hydrogenating the unsaturated part of all or part of the unsaturated ester used as a raw material. Therefore, the "hydrogenated ester" in this specification is generally called "Saturated ester", when there are several unsaturated groups in the unsaturated ester of the raw material, it includes not only all hydrogenated substances (ie saturated esters), but also some hydrogenated substances, and these saturated esters / unsaturated ester For example, when allyl acetate is used as the raw material containing unsaturated group, the equivalent hydrogenated ester is n-propyl acetate, and 1,3-butadiene acetate is used as the unsaturated group. In the case of esters, equivalent hydrogenated esters refer to n-butyl acetate, n-1-butene acetate, n-2-butene acetate, n-3-butene acetate, and mixtures thereof. Since ancient M In the past, saturated esters such as n-propyl acetate, isobutyl acetate, and n-butyl acetate are mostly used as solvents, solvents, or reaction solvents, and are industrially important compounds. These saturated esters are generally obtained by borrowing It is made by condensing an equivalent alcohol with a carboxylic acid and esterifying it with M. However, in this ester group, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) applies to this paper size ----, -&lt; -----, • Install (please read the precautions on the back before filling this page) ---- Order i — Line ·! Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 __B7___ V. Description of the Invention (2) (Please read the precautions on the back before filling out this page) It is necessary to remove the by-product water To the outside, the equilibrium state of the reaction cannot be inclined to the product (ester) side, and it is not possible to obtain a favorable raw material conversion rate or reaction speed in industry. To solve this problem, for example, Japanese Patent Application Laid-Open No. 5-194318 Various proposals. However, the industrial production method of carboxylic acid esters through esterification of yeast and carboxylic acid in this bulletin must have more complicated reaction equipment or reaction engineering problems than other reaction methods. In addition, by fermentation and The condensation of carboxylic acid and K esterification reaction can not avoid the formation of water in the system. However, since the latent heat of evaporation of water is much larger than that of other organic compounds, a lot of energy is consumed by distillation and separation of water. Difficulties exist. In addition, an unsaturated group-containing ester containing unsaturated groups such as allyl, methallyl, and vinyl on the alcohol portion of the ester can pass through the equivalent alkene and carboxylic acid oxidized carboxyl groups. Chemical reaction and other industrial production. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, especially in the presence of a palladium catalyst, it is known to produce unsaturated esters containing unsaturated groups by gas-phase reaction of alkenes, oxygen and carboxylic acid K. There are many known documents about this, for example, Japanese Patent Publication No. 44-29 046, Japanese Patent Publication No. 48-23408, Japanese Patent Publication No. 50-28934, and Japanese Patent Publication No. 1-197457. Among them, Japanese Patent Application Laid-Open No. 1-197457 discloses that through the reaction of the corresponding olefins with oxidized carboxylic acids of carboxylic acids, extremely high yields can be obtained, and high space-time yields can be used to manufacture esters containing unsaturated groups in the industry. In addition, in addition to the above-mentioned allylic ester containing an unsaturated group, in addition to the oxidative carboxylation reaction of an equivalent alkene with a carboxylic acid, the propyl-type chloride may be reacted with a carboxylic acid or a carboxylic acid salt. The reaction is based on allyl-type enzymes, a paper size, and a Chinese paper standard (CNS) A4 (210 X 297 mm). 499421 A7 _B7_ V. Description of the invention (3) Condensation with carboxylic acid, etc. , Can be produced by M industry. Therefore, various methods for preparing hydrogenated (especially saturated) hydrogenation reactions for unsaturated allyl-containing esters such as allyl-type esters which are readily available are reviewed. The hydrogenation catalyst used in the hydrogenation reaction of unsaturated esters is selected from the periodic table (revised by the International Pure and Applied Chemical Coupling Inorganic Chemistry Nomenclature (1989), the same applies to M), group 8 elements, 9 It is known that the golden cymbals of the family element and the group 10 element are effective. In addition, a problem with the method using the gold catalyst is that the raw material contains an unsaturated hydrodecomposition containing an unsaturated group. In other words, the allyl ester represented by the general formula ，, or the allenyl group represented by the general formula 在, has a catalyst containing gold sulfonium selected from group 8 elements, group 9 elements, and group 10 elements. It is hydrogenated in the presence of hydrogen. When producing saturated esters, the esters containing unsaturated groups in the raw materials undergo a hydrogenation decomposition reaction, and the equivalent carboxylic acids and alkanes that generate by-products are known (refer to "Applications of Contact Hydrogenation-Organic Synthesis" I ", Tokyo Chemical Associates, issued April 10, 1987, No. 1 and No. 1, page 116). &lt; Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

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R 〇 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 499421 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4)

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In order to solve this problem, the method of using palladium metal as a catalyst is known in terms of controlling the hydrogenolysis reaction of the enol-based ester (refer to the above-mentioned "Application of Contact Hydrogenation-Organic Synthesis" on page 116) . In addition, it is known to control the allyl-type hydrogenation decomposition reaction using 鍩 金 鍩 as a catalyst system (WF · Berkowitz, I.Sasson, PS · Sampathkumar, J · Hrable, SC Choudhry, D. Pierce * Tetrahedron Lett., 1 979, p. 1641) 0 However, according to the experiments by the present inventors, it is known that the above catalysts can effectively control hydrogenation for the hydrogenation of an enol-based ester or an allyl-based ester. The decomposition reaction cannot effectively control the hydrogenation reaction for the hydrogenation of these two unsaturated ester-containing esters. In addition, a method for producing a saturated ester from an unsaturated group-containing ester using a nickel-based hydrogenation catalyst is disclosed (Japanese Patent Application Laid-Open No. 9-1 94427). Compared with the method using palladium-gadolinium as a catalyst and the method using gadolinium as a catalyst, this bulletin can effectively control the hydrogenolysis reaction by using a nickel bar hydrogenation catalyst. However, the inventors The method actually carries out the hydrogenation reaction. When trial production of equivalent saturated esters, it can be seen that although there is a certain degree, it is accompanied by the decomposition reaction of equivalent pinane and equivalent carboxylic acid (that is, the hydrogenation of raw materials-6- (Please read the back first) Please pay attention to this page before filling in this page) Engine installation -------- Order --- Line __ This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the consumer cooperative 499421 A7 B7_ V. Description of the invention (5) Solution reaction). More specifically, it is known from experiments by the present inventors that even when the method described in Japanese Patent Application Laid-Open No. 9-1 94427 is used, it is not easy to easily obtain a high-purity product specification of saturated esters used as a solvent or a reaction solvent. Saturated ester. In other words, the allowable amount of the amount of carboxylic acid generally required as a product specification of saturated esters is a concentration at 50 pPm M, and the purity of the saturated ester is 99.5% by mass M. In other words, the production of carboxylic acids by this hydrogenolysis reaction is a very important issue in terms of the quality of products of saturated esters. In addition, in general, it is not easy to separate the unsaturated sulfonium (e.g., allyl acetate) and the saturated ester (e.g., n-propyl acetate) of the product by simple distillation, so it is necessary to achieve the product specifications. I M multi-stage distillation. Considering these times and in order to simplify the precision engineering after the reaction, the conversion rate of the unsaturated ester containing M is 99.8S5M, and the selectivity of the carboxylic acid of the by-product is very small (the selectivity of the carboxylic acid is 2. OS! M), and improve the selectivity to hydrogenated esters (especially saturated esters) (selectivity of saturated esters is 9 8. Ο Κ) is very good. However, for example, in the above-mentioned Japanese Patent Application Laid-Open No. 9-1 94427, there is no description of the use of a nickel bar hydrogenation catalyst. When a saturated ester is produced from an unsaturated group-containing ester, the conversion rate of the unsaturated group-containing ester is 99.8¾ M. At this time, the selectivity of the saturated ester and the carboxylic acid each reached 98,0% Μ, and below 2.0¾. An object of the present invention is to provide a method for efficiently producing a hydrogenated ester by controlling the hydrogenation decomposition of a side reaction of a hydrogenation reaction when producing an equivalent hydrogenated ester by a hydrogenation reaction of an unsaturated group-containing ester. -7- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) · I ------ Order ------ --- Line win 499421 A7 B7 V. Description of the invention (6) In order to solve the problem of inversion, the inventors repeatedly studied the hydrogenation reaction of esters containing non-planar and radicals using hydrogenation catalysts, and found that the raw materials for the hydrogenation reaction The concentration of unsaturated esters and the specific ingredients contained in them, or the specific parameters of hydrogenation catalysts, are extremely relevant to the hydrogenation reaction. The present inventors first discovered that the hydrogenation reaction of an unsaturated group-containing ester is diluted with an inert solvent and the reaction is carried out, and almost no hydrogenolysis reaction occurs, and a hydrogenated ester, especially a saturated ester, is obtained in a high yield. The method for producing a hydrogenated ester according to one aspect of the present invention is based on the above-mentioned findings. More specifically, an unsaturated group-containing ester not included in the general formula (1) is hydrogenated in the presence of a hydrogenation catalyst to produce an equivalent. In the case of a hydrogenated ester, the unsaturated group-containing ester is diluted with an inert solvent to perform a hydrogenation reaction. (Please read the notes on the back before filling this page) R 3

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R 1, R 2, R 3, R 4, R 5 僳 represents any alkyl group with a sulphur number of 1 to 10 and any alkenyl group with a carbon number of 1 to 10 Or a hydrogen atom, which may be the same or different, and the alkyl or alkenyl group may have a linear or branched fluorene. R 6 傜 is an arbitrary alkyl group having a sulfonic number of 1 to 10, and may have a linear or branched fluorene. Η Like 0 or 1). The manufacturing method of the present invention having the above-mentioned structure, as the above-mentioned inventors found, by the method of the winding technology, the hydrogenation reaction is actually performed, and the production phase is trial-produced. A paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297). (Mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 __B7__ V. Description of the invention (7) When the saturated ester is used, the raw material liquid containing the unsaturated group-containing ester shown in the general formula 视 is considered to contain The unsaturated ester concentration depends on the decomposition reaction of the equivalent alkane and the corresponding carboxylic acid. Herein, the "equivalent alkene" in the present specification refers to an alkene which is a raw material when an unsaturated group-containing ester M is subjected to a carboxylation reaction to generate hydrogen. For example, when the unsaturated group-containing ester is allyl acetate, the equivalent olefin means propylene. The "equivalent paraffin" in this specification refers to a pinane produced by a hydrogenolysis reaction during a hydrogenation reaction of an unsaturated ester. For example, when the unsaturated group-containing ester is allyl acetate, the equivalent alkane means propane. In addition, the "raw material liquid containing an unsaturated group-containing ester" in this specification is used as a raw material for the reaction process of a corresponding hydrogenated ester, and contains a liquid containing an unsaturated group-containing ester and / Or gas, so it refers to those who remove inert gases such as nitrogen or paraffin and hydrogen. In this regard, Japanese Patent Application Laid-Open No. 9-1 94427 discloses a conventional document, and in particular, there is no description of an unsaturated group-containing ester in the hydrogenation reaction of the unsaturated group-containing ester in the raw material liquid. Concentration, equivalent to the yield or selectivity of saturated esters. The present inventors have also found that when the concentration of the osmic acid contained in the raw material containing the allyl ester exceeds a certain amount, the hydrolytic reaction is promoted. In other words, according to another aspect of the present invention, when a hydrogenation catalyst for an allyl ester (η = 1) represented by the above general formula (I) is used to perform a hydrogenation reaction to produce a corresponding hydrogenated ester, The method for producing a hydrogenated ester at a concentration of carboxylic acid contained in the allyl ester-containing raw material at lwtiKM is shown. -9- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read Note 3 on the back before filling this page)-· I ------ Order ··- ------ Line ^ --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 Α7 Β7 V. Description of the invention ()

(Wherein R1, R2, R3, R4, and 1-5 represent any alkyl or hydrogen atom having 1 to 10 carbon atoms, each of which may be the same or different, and the alkyl group may have a straight or branched chain; R6 represents an arbitrary alkyl group having 1 to 10 carbon atoms, and may be a straight chain or a branched chain. In addition, conventional documents starting from Japanese Patent Application Laid-Open No. 9-1 94427 are not described in allyl esters. In the hydrogenation reaction, especially the carboxylic acid content in the raw material containing the allyl ester and the equivalent yield or selectivity of the hydrogenation fermentation, the present inventors have repeatedly studied the hydrogenation reaction of the unsaturated group-containing ester. Catalyst (especially various parameters of the catalyst), as a result, it was found that the method for hydrogenating unsaturated ester-containing esters to produce equivalent hydrogenated esters contains at least one element selected from Group 8 elements and Group 9 of the periodic table. And the catalyst of gold element of group 10 element, the catalyst has an acid point of 1.OXlO · 1 millimolar / gM, as measured by the Tetraper ature Programmed Desorption method (hereinafter referred to as "TPD method"). In the following cases, there is almost no decomposition reaction accompanying the unsaturated group-containing ester of the raw material. Yield obtained hydrogenated ester. Another form of the hydrogenation catalyst of the present invention is a method for producing hydrogenated esters represented by the general formula (1) to hydrogenate an ester containing an unsaturated group represented by the general formula (1). 10- This paper is in accordance with China National Standard (CNS) A4 Specifications (210 X 297 mm) I ------------------- Order --------- line (Please read the precautions on the back before filling in this (Page) 499421 A7 B7

V. Description of the invention (A catalyst containing at least one metal selected from Group 8 elements, Group 9 elements and Group 10 elements of the periodic table is used, and the acid point of the catalyst is 1.0 × 104 mol / gM. R 3 (1) 〇 (where n represents 0 or 1; R1, R2, R3, R4, R5 represent independent alkyl groups having 1 to 10 carbon atoms and olefins having 1 to 10 carbon atoms Radical or hydrogen atom; R6 is an arbitrary alkyl group having 1 to 10 carbon atoms) (Please read Note 3 on the back before filling this page)

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R (2) 〇 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where n is 0 or 1; R6 is any alkyl group with 1 to 10 carbon atoms; R7, R8, R9, R1 (D 'R11 series Each is an independent alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or a hydrogen atom) so that gold containing at least one element selected from Group 8 elements, Group 9 elements, and Group 10 elements of the periodic table The hydrogenation catalyst of rhenium has a small acid point, which can effectively inhibit the hydrogenation decomposition reaction caused by the hydrogenation reaction of enol-type esters or allyl-type esters, and it can be hydrogenated with a high selectivity to K. What I do n’t know. -11 A paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_ V. Description of the invention (^ The present invention provides the above The production method of hydrogenation catalyst is characterized by the following first process to second process. <First process> A metal compound is supported on a carrier having an acid point of 1.0X 10 · 1 mmol / gM. , A process for obtaining a carrier carrying a gold tincture compound; <the second project> loading the proceeds from the first project A process for preparing a gold compound which is a carrier of a compound to prepare a hydrogenation catalyst. In addition, the present invention provides the use of the above-mentioned hydrogenation catalyst to hydrogenate an unsaturated group-containing ester represented by the general formula ⑴ to prepare the general formula ⑵ The method for producing the hydrogenated ester of the hydrogenated ester shown. Brief description of the drawing Figure 1 is a flow chart showing the form of a device system for implementing the method for manufacturing a hydrogenated ester of the present invention. Figure 2 is an ion exchange resin used in the examples of the present invention Flow chart of the processing device and form. Each reference symbol in the figure has the following meanings: 1 Supply pipe containing unsaturated esters 2 Hydrogen supply pipe 3 Recovery hydrogen ester supply pipe 4 Heater 5 Reactor 6 Catalyst Packing layer 7 Liquid extraction tube after reactor 12-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I --------------- --- Order --------- line (please read the precautions on the back before filling out this page) 499421 A7 B7 V. Description of the invention (M printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 8 cooler 9 Rapid gas piping 10 General-purpose piping for generating liquid flow 11 Piping for producing liquid extraction 21 Ion exchange resin input piping tower 22 Hina exchange resin 23 Hina exchange resin layer 24 Drain piping from ion exchange resin 25 Distillation tower piping tower 26 Distillation Column 27 The bottom liquid discharge pipe of the distillation tower 28 The top liquid discharge pipe of the distillation tower is the best form for carrying out the invention. The invention will be described in detail below with reference to its requirements. The ratio of the amount in the figure is the plant part J and the plant> In particular, it is limited to the basis of weight (and mass). 0 (unsaturated ester) In the method for producing a hydrogenated ester of the present invention, the following general formula (1 ) Contains unsaturated groups Esters &gt; Hydrogenated in the presence of a hydrogenation catalyst to produce equivalent hydrogenated esters 〇 By this example, for example, the hydrogenated esters shown in the general formula ⑵ can be obtained as follows

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(1) (Please read the notes on the back before filling this page) W Pack ------- Order ---- Line, _ 〇 This paper size is applicable to China National Standard (CNS) A4 (210 X 297) (Mm) 499421 A7 B7 V. Description of the invention (12 sulphur, alkane, 10 of any

R

2 R

3 R

4 R

5 R ο Count the number of each disc, the original hydrogen alone or the meaning of each alkene ~ the same as the number of phases} or sulfo 1 with the same or not shown C is for the branch or the straight alkene Alkanes

6 R η chain branched or straightened with any alkane meaning ο image system

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11 R protons or alkenes ο Examples of ester bases and sulphur-containing compounds are used, so that 1 = n = the cost, for example

2 E = η

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3 R ester bases and saturated

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3 R Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs.

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5 R and 4 R

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4 R and ester bases and unsaturated esters, alkenyl 7 ester diyl butylene I I ethyl 3 1

5 R II η When the methyl group is 1 R, the original hydrogen of the ester butylene is gold. For example, II η

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2 R bases are limited by 3 β. These and 1 are not applicable. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm).

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When U &gt; 1, the atom proton u is chlorine i; f is 3 all *, R

2 R Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ V. Description of the invention (Ί Specific examples of the above esters containing unsaturated groups, such as allyl acetate, allyl propionate, methyl allyl acetate , Methylallyl propionate, butenyl acetate, butenyl propionate, vinyl acetate, vinyl propionate, 1,3-butadiene acetate, 1,3-butadiene propionate, etc. Preferably, more preferred are allyl acetate, methallyl acetate, butenyl acetate, and 1,3-butadiene acetate. The following acid point system has an acid point of 1.0 × 10 4 In the form of hydrogenation catalyst under millimoles / gK, specific examples of esters containing unsaturated groups where n = l, such as allyl acetate, allyl propionate, methyl allyl acetate, propionic acid Methylallyl, butenyl acetate, and butenyl propionate are preferred, and allyl acetate, methylallyl acetate, and butyl acetate are more preferred. In addition, η = 0 contains unsaturated groups Specific examples of the esters, such as vinyl acetate, vinyl propionate, 1,3-butadiene acetate, 1,3-butadiene propionate, 1-methyl-1-propenyl acetate, propylene Acid 1-form 1-propenyl and the like are more preferred, and 1,3-butadiene acetate and 1-methyl-1-propenyl acetate are more preferred. The unsaturated group-containing ester is an allyl group having η = 1 In the case of type esters, in the form of the present invention in which the carboxylic acid content in the raw material containing the allyl type ester is 1% by mass, the preferred allyl type esters are R1, R2, R3, R4 and

All Rs are allyl esters of hydrogen atoms, R3 is methyl, R1, R2, R4, and Rs are all methacrylic esters of hydrogen atoms, R1 is methyl, R2, R3, R4, and R5 are all hydrogen atoms of butyl Enoester. Specifically, for example, allyl acetate, allyl propionate, methallyl acetate, methallyl propionate, butenyl acetate, butenyl propionate, etc. are preferred, and more preferred is allyl acetate Propyl ester, methyl allyl acetate. 15- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -1 ------ Order ------ --- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ V. Description of the invention (Ί Here, the "raw material containing allyl esters" in this specification is used for the synthesis of equivalent hydrogenated esters The raw materials for reaction engineering are used in the hydrogenation reaction, which refers to the removal of inert gases such as nitrogen or paraffin and hydrogen from liquids and / or gases containing allyl esters fed into the reactor. The "concentration of carboxylic acid contained in the raw material" refers to the concentration of carboxylic acid for the removal of inert gas such as nitrogen, paraffin, and hydrogen from a liquid and / or gas containing an allyl ester. When the liquid system is allyl acetate: n-propyl acetate = 1: 10 Ut / wt), the "raw material containing allyl ester" means allyl acetate: n-propyl acetate = l: 10 Ut / wt), and the concentration of carboxylic acid at this time is p-allyl acetate: n-propyl acetate = 1: 10 Ut / wt) For mixed liquids. The method for obtaining the composition ratio in the composition in the present invention is preferably performed by M by the internal standard method of the gas chromatography method described below. (Specific examples of hydrogenated esters) Specific examples of esters when the product of η = 1 in the above general formula ， include, for example, n-propyl acetate produced by hydrogenation of allyl acetate, and n-propyl acetate produced by allyl propionate. N-propyl propionate produced by hydrogenation, isobutyl acetate produced by hydrogenation of methyl allyl acetate, isobutyl propionate produced by methyl allyl propionate, and butyl acetate The n-butyl acetate produced by the hydrogenation of olefinic esters, and the n-butyl propionate produced by the hydrogenation of propylene butylene esters are not limited to these. Further, specific examples of hydrogenated esters when n = 0 in the above general formula (I) of the same product, for example, ethyl acetate generated by hydrogenation of vinyl acetate and ethyl propionate generated by hydrogenation of vinyl propionate With acetic acid 1, this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note 2 on the back before filling this page)-I ------ Order-- -------- The line is 499421 A7 B7 91ΎΓΊ Year, month, day and five. Description of the invention ("Turtle _ Printed 3-butane and these 1-methylene propionates by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1-methyl but not subject to the second method of mixing methene in an industrially unsaturated propyl-type propyl type; the first method is to make the hair ~ the third method will only produce chlorine-containing and hydrogenation of the allyl ester. A mixture of the resulting n-butyl acetate and 3-butenyl acetate, and n-butyl ester, 3-butenyl propionate, and the mixture thereof by hydrogenation of 1,3-butadiene propionate , 2-Butyl acetate produced by hydrogenation of 1-propenyl acetate, 2-propionate produced by hydrogenation of propyl-1-propenate Butyl esters, etc. are limited. Production method of unsaturated esters) Propyl esters are esters containing unsaturated radicals in the first place. Generally speaking, they can be produced by three methods described below. In the method for producing a group-containing ester, one example of the olefinic ester is explained by way of example (therefore, when the description of the method of production does not violate the purpose, "enyl ester" can be broadly interpreted as "ester containing unsaturated group" The first method is a method in which the equivalent gas of pinene, oxygen, and a carboxylic acid is reacted in a gas phase in the presence of a palladium catalyst; the method is to make an allyl chloride and a carboxylic acid or a phosphonate The reaction method 3 is a method produced by the esterification reaction of the condensation of an allyl alcohol with a carboxylic acid. The allyl ester that can be used in the raw materials can also be applied by any of the methods described above. Manufacturer. Among the allyl esters produced by the above-mentioned second method, carboxylic acids that are not used as acid components and hydrochloric acid may be generated. In addition, the compounds may be the cause of the decrease in the activity of the hydrogenation catalyst. When the allyl ester is produced by the third method described above, the Except for the water of the product, the equilibrium state of the reaction is not -17- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Order --------- Liantai 499421 A7 B7_ V. Description of the invention (Ί (Please read the notes on the back before filling this page) The method is inclined to the product (allyl ester) side, industrially It is not easy to obtain a favorable raw material conversion rate or reaction speed. Therefore, through the esterification reaction, the industrial production of allyl esters requires complicated reaction equipment or reaction engineering when other production methods are used, and the distillation separation of water also requires much. Consume energy. In these respects, in the method for producing a hydrogenated ester of the present invention, a mixed gas composed of equivalent alkenes, oxygen, and a carboxylic acid is subjected to a gas phase reaction in the presence of a palladium catalyst (first method), Allyl esters produced at low prices in the industry are extremely advantageous as raw materials. (Gas raw material) In the method for producing a hydrogenated ester of the present invention, a gas system for supplying reaction tritium uses a gas containing at least hydrogen. In addition to hydrogen, nitrogen or rare gas can be used as the diluent gas, if necessary. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs There is no particular limitation on the hydrogen gas that can be used as the raw material in the production method of the hydrogenated ester of the present invention. Generally, it can be a commercially available product. In addition, the amount of hydrogen supplied is the theoretical amount of hydrogen necessary for the purpose of producing the intended hydrogenated ester (such as a saturated ester) from an ester containing an unsaturated group, and the theoretical amount is preferably 1.1 to 3.0 times the theoretical amount. 1.1 to 2.0 times the amount is best. The amount of hydrogen supplied equal to or smaller than the theoretical amount is due to the occurrence of a side reaction such as a hydrogenolysis reaction, and the amount of hydrogen consumed by the side reaction tends to cause the original reaction to be insufficient. In addition, when the amount of hydrogen supplied is excessive (for example, an amount larger than 10.0 times the theoretical amount), there is a tendency that the economy is not favorable. (Hydrogenation catalyst) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ V. Description of the invention (M This invention consists of unsaturated groups The catalyst system M used in the production of the equivalent hydrogenated esters of the ester contains a group 8 element and a group 9 element selected from the weekly table (revised edition of the International Pure and Applied Chemistry Joint Inorganic Chemical Nomenclature (1 989), which is the same below). Catalysts of Group 10 elements are preferred. Elements selected from Group 8 elements, Group 9 elements, and Group 10 elements of the periodic table such as iron, ruthenium, iron, cobalt, osmium, iridium, nickel, palladium, and uranium. Elements such as palladium, rhodium, ruthenium, nickel. Among them, palladium, osmium, and ruthenium are more preferred. The raw material compounds selected from the metal components of Group 8 elements, Group 9 elements, and Group 10 elements of the periodic table can generally use nitric acid, Inorganic acid salts such as sulfuric acid and hydrochloric acid can be used, but organic acid salts such as acetic acid, hydroxides, oxides, and mixed salts can also be used. More specific examples of the raw material compounds of gold tincture include F1C1 2, FeC1 3, and Fe (NO 3) 3, FeSO 4, Fe 2 (SO 4) 3 and other inorganic compounds, Fe (CH3CH0HC00) 2,

Organic compounds such as Fe (CH3 COCHCOCHs) 3. Ruthenium compounds include, for example, inorganic compounds such as RuC13, organic compounds such as Ru (CH3C0CHC0CH3), and coordination compounds such as ruthenium chloride and triruthenium dodecylcarbonyl. Examples of the hungry compounds include inorganic compounds such as OsC 1 3. Examples of cobalt compounds include inorganic compounds such as COCI2, Co (N〇3) 2, and CoS04,

Co (CH 3 C00) 2, Co (CH 2 C0CHC0CH 3) 2,

Co (CH3 C0CHC0CH3) 3 and other organic compounds. Europium compounds include inorganic compounds such as RhCls, Rh (N03) 3, Rh2 (S04) 3, organic compounds such as Rh (CH3C0CHC0CH3) 3, and coordination compounds of tetrarhodium (M) dodecylcarbonyl. Iridium compounds include, for example, IrCl3 -19- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------------------ Order ---- ----- Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ V. Description of the Invention (Ί, I r C 1 4 and other inorganic compounds. Chain compounds For example, there are inorganic compounds such as Ni C 1 2 and Ni S 0 4, and organic compounds such as Ni (CH3 C00) 2 and Ni (CH3 COCHCOCH3) 2. Palladium compounds such as PdCl2, Pd (H03) 2, Pd2 S〇4,

Na2PdCl4 and other inorganic compounds, Pd (CH3C00) 2,

Coordination compounds such as organic compounds such as Pd (CH3 COCHCOCHs) 2, tetraamminepalladium U) chloride and the like. Examples of the platinum compound include inorganic compounds such as K2 PtCl4 and PtCl2, and organic compounds such as Pt (CH3C0CHC0CH3) 2. Among the above, in terms of suppressing the activity balance between the hydrogenation reaction and the hydrogenation reaction, preferred metal compounds include ruthenium compounds, osmium compounds, and palladium compounds. The hydrogenation catalyst used in the present invention to produce an equivalent hydrogenated ester from an unsaturated group-containing ester may be a separate element (or compound), or it may be supported on a carrier as required. For example, when a fixed-layer reaction device is used as a carrier, a large metal surface area where a contact process between a hydrogenation catalyst and an ester containing an unsaturated group can be obtained. Among the catalysts supported on the carrier, it is preferable that the alumina carrier supports the element (or a compound containing the element) selected from Group 8 elements, Group 9 elements, and Group 10 elements of the periodic table, and is selected from the periodic table. Group 8 elements, group 9 elements, and group 10 elements are particularly preferably palladium, osmium, and ruthenium. (Acid point of the catalyst) In the method for producing the hydrogenated ester of the present invention, in order to more effectively suppress the hydrogenolysis reaction, at least one element selected from Group 8 elements, Group 9 elements and Group 10 elements of the periodic table is contained. Among the catalysts of the element, the catalyst M mirror-20- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------------- --- Order -------- Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ V. Description of the invention (Ί One-temperature demelting method (Temperature Programmed Desorption;-· K is abbreviated as "tpb method") The acid point κι.oxio measured in millimoles per gram K is better. As long as the hydrogenation catalyst that can be used in the present invention is the MH-TPD method The measured acid point may be a hydrogenation catalyst containing at least one metal selected from Group 8 elements, Group f elements, and Group 10 elements of the periodic table at 1.0 × 40 mol / gM, and there is no particular limitation. When using a catalyst having an acid point greater than 1.0 XKT1 millimolars / g, it is obtained by the hydrolytic decomposition of an unsaturated group-containing ester as shown in the general formula 原料 of the raw material. The selectivity of raw carboxylic acids tends to be higher. The acid point is better at M0.5X 10 mmol / gK, and more preferably 0.3X104 mmol / g K. Catalyst The theoretical factors of the acid point and the hydrogen decomposition reaction are not clear at present, but it is speculated by the present inventors that when the K catalyst causes the hydrogen decomposition reaction, the radical cracking reaction on the K catalyst and the Sn 1 ion reaction, Either the Sm i-type reaction or the Sn 2 type reaction is dominant, or two types of M-type mechanisms are in parallel. At this time, from the insights of the present inventors, it is estimated that when there are many acid sites in the catalyst, the acid contains unsaturated The electron density of the terminal carbon of the alkyl ester (or the carbon bonded to the oxygen of the ester) and the oxygen of the ester decreases due to the adsorption of oxygen on the ester of the radical, resulting in the occurrence of free radical cracking reactions and Sn. I type reaction or Sn type 2 reaction, the proportion of hydrogenolysis reaction is increased. (Ammonium-TPD method) In the present invention, the acid point M of the catalyst is preferably measured by the ammonium-TPD method. -21- This paper scale Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ------------------- ^ --------- (Please read the back first Please pay attention to this page and fill out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_ V. Description of the invention (1 The ammonium-TPD method is described as follows. First, the ammonium molecule is adsorbed on the catalyst, and then borrowed The ammonium is detached by increasing the temperature M. At this time, when the adsorption plutonium having several adsorption species with different strengths becomes an irreversible adsorption state, the temperature of the catalyst is decreased and increased, and the adsorption species with weak surface bonds are sequentially separated. When the adsorption bonding force is much different, the dissociation reaction occurs at different temperature ranges, and the different species are distinguished under the condition of no re-adsorption of dissociated molecules. In the present invention, it is better to explain the detachment process of adsorbed molecules based on this principle. (For a detailed description of the ammonium-TPD method, please refer to the journal "Catalyst", edited by Catalyst Society, Vol. 24, Η〇3, p. 225 ~ 230 pages, published June 30, 1987). In this specification, it is preferable to use a vacuum exhaust type TPD device for the measurement of the acid point. The value of the acid point in this specification is a value obtained by dividing the number of ammonium molecules separated in the range of 230 ¾ to 600 1C during measurement under the measurement conditions described in the following examples, divided by the usage amount of the sample to be measured. The hydrogenation catalyst system M having the specific acid point described above preferably contains at least one metal selected from Group 8 elements, Group 9 elements, and Group 10 elements of the periodic table. Specific examples of the metal include iron, ruthenium, and osmium of Group 8 elements of the periodic table, cobalt, osmium, and iridium of Group 9 elements, and palladium and platinum of Group 10 elements, and are not particularly limited. A preferred gold tincture is at least one gold tincture selected from the group consisting of palladium, rhodium, and ruthenium. (Carrier) In the present invention, a hydrogenation catalyst carrier can be carried on a carrier as necessary as described above. The carrier at this time is generally not particularly limited as a substance (for example, a porous substance) used as a carrier for a catalyst load. Compared with the paper size of this carrier, it is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ------------------- Order ------- -Line (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ V. Description of the invention (2i specific examples such as silicon dioxide (SiO 2), alumina (A 1 2 0 3), titanium oxide (Ti0 2), diatomaceous earth, carbon, or a mixture of these, etc. In terms of ease of processing, it is particularly carried on a formed support selected from Group 8 of the periodic table. Elements such as element, group 9 element, and group 10 element are advantageous. Examples of the formed carrier include those having various shapes such as pellets, spheres, etc. The specific surface area of the carrier used in the present invention is not particularly limited as required. As far as the catalyst metal can be easily dispersed, K has a high specific surface area. More specifically, the specific surface area value by the BET method is preferably 10m2 / g ~ 1000m2 / g. 30m2 / g ~ 800 m2 / g (especially K50m2 / g ~ 500m2 / g). In addition, the "specific surface area by the BET method" in this specification is by Brunauer , Emmett, and Tel ler and others found that the specific surface area was determined using an adsorption isotherm (for a detailed description of the BET specific surface area, refer to, for example, "Experimental Chemistry Lecture 7 Interface Chemistry", Maruzen (Korea), Showa 43 Issued on August 10th, 3rd edition, 3rd brush, "11.5 Catalyst Surface Area Determination Method" under page 489 K). In addition, the total pore volume of the carrier is not particularly limited, MO. 05ml / g ~ 6.5ml / g is more preferred, and more preferably 0.1ml / g ~ 5.0ml / g (especially 0.5ml / g ~ 3.0ml / g). Moreover, the "full pore volume" in this specification is borrowed. An amount defined by the full volume of the pores of the sample lg obtained from the adsorption amount of the saturated vapor pressure (for a detailed description of the full pore volume, refer to "Catalyst Engineering Lecture 4 Catalyst Basic Measurement Method", (Shares) Local People's Library, July 30, Showa 39, first edition, "69, 1, 3, and 2 full pore volume (C) after the saturation vapor pressure is used to determine the paper size. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ----------- installation -------- order --------- line (please first Read the back Please fill in this page again.) Printed by 499421 A7 __B7_ by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (item 1). (Carrier shape) There is no particular shape of the carrier that can be used in the present invention. Restrictions may be appropriately selected from conventional shapes. As far as the uniformity of the internal pressure of the reactor, pellets, spheres, hollow cylinders, wheels with spokes, and honeycomb-shaped monolithic tunnels with parallel flow tunnels can be used. For the medium carrier or the foamed ceramic with open cells, pellets and spheres can be used in terms of the simplicity of the manufacturing method. The carrier used in the method for producing the hydrogenated catalyst of the present invention is used when the negatively loaded catalyst on the carrier is scattered and stacked on the catalyst layer, and the pressure is too low to be used, and compared with the total capacity of the scattered accumulation during the scattered accumulation It is preferred to have a very high geometric surface area. In this regard, a more specific example is that the catalyst carrier K has a size of 0.5mm to 5.〇1! 1111, and the more preferable one has a size of 1. (^ 111 ~ 4.51〇111. Production method) The production method of the hydrogenation catalyst of the present invention is not particularly limited. In terms of simplicity of production, the above-mentioned catalyst having a specific acid point M is preferably produced by the following method. The production method of the hydrogenation catalyst contains at least the following The first project and the second project. The first project: a process in which a gold compound is carried on a carrier having an acid point of 1.0 × 10 4 mmol / gM to obtain a carrier carrying a metal compound; the second process : The project of relocating the metal compound carrying the metal compound-carrying carrier obtained in the first project mentioned above to the production of hydrogenation catalyst. -24-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ) ----------- Installation -------- Order --------- (Please read the precautions on the back before filling this page) Employees of the Bureau of Intellectual Property, Ministry of Economic Affairs Printed by the Consumer Cooperative 499421 A7 _B7_ 2 3 V. Description of the invention () (1st project) The 1st project "the 1st project" means that the metal compound is carried on the The process of preparing a carrier carrying a metal compound on a carrier having an acid point of 1.0 × 104 millimolars / g or less is preferably performed by using a metal compound dissolved in a liquid. The liquid in which the metal compound is dissolved so that The metal compound is highly soluble and preferably absorbs a carrier liquid (such as an aqueous liquid). The "aqueous liquid" in this specification means a liquid having a homogeneous phase with water as an essential component. As for the dissolution of the metal compound In terms of properties, the aqueous liquid (based on the mass of the entire aqueous liquid) is preferably 5 G% or more, more preferably 75% or more, such as pure water, various aqueous solutions (such as acidic aqueous solutions, Alkaline aqueous solution) and a mixed solution of water and other aqueous liquid solutions (such as a mixed solution of pure water and alcohol), etc. (Loading method of catalyst) The method for loading the hydrogenation catalyst of the present invention is not particularly limited, and may be Co-precipitation using conventional knowledge (For details about this co-precipitation, refer to "Catalyst Engineering Lecture 5 Catalyst Modulation and Test Method", Local People's Library, Issue 3, Showa, September 3, 40, p. 8 To "Seven, one, six precipitation purity and co-precipitation" method), forced evaporation method or impregnation method (e.g., "contact hydrogenation reaction-organic synthesis" Application- ", Tokyo Chemical Co., Ltd., issued on April 10, 1987, No.1, No.1 brush, and" 1, 1, 2-Impregnation method "on page 5 and later). Regarding the control of the carrier In terms of the loading state of metal compounds, it is better to use the impregnation method or spray to force the loading method. -25- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ί-- -l · — l · --l--install ----- ^ ---- order --------- (Please read the notes on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumption Cooperative 499421 A7 B7 _ 5. Description of the invention (In addition, if necessary, a process for dissolving the metal compound carrying the metal compound carrier on the liquid used for the catalyst can be provided. By providing this insolubilization process, the advantage of preventing the elution of the metal compound can be obtained. The insolubilization method used at this time is not particularly limited, and it is preferable to add a basic substance such as NaOH, Na2SiO3, or Ba (OH) 2 to convert it into an oxide or hydroxide without dissolving. In addition, after the negative catalyst is carried on the carrier, it is washed with K as needed, and K 20 ° C ~ 250 1 is preferably dried. By providing this water-washing process, it is possible to obtain the advantage of removing excess alkaline substances and the like. (Second process) Next, the second process of the above-mentioned process will be described, even if the metal compound carrying the metal compound carrier obtained in the first process is transferred to the original process to prepare a hydrogenation catalyst. There is no particular limitation on the progress of this second project, and it can be appropriately selected from conventional methods of relocation. Specific examples of the original migration method, such as the conventional liquid phase migration treatment, such as the use of NaBH, or tritium relocation agent liquid phase migration treatment or the conventional gas phase migration treatment, such as heating under hydrogen gas flow Gas phase relocation processing is not limited by these (for details about the method of relocation, refer to, for example, Japanese Patent Application Laid-Open No. 7-89 896). (Loading amount) There is no particular limitation on the loading amount of the metal component selected from Group 8, Group 9, and Group 10 elements of the periodic table on the carrier in the present invention. Regarding the metal cost or catalyst activity selected from Group 8 elements, Group 9 elements, and Group 10 elements of the periodic table (based on the mass of the entire catalyst) M is adjusted to 0.01% by mass -26-This paper standard applies to China Standard (CNS) A4 specification (210 X 297 mm) -------- Order --------- Hua (Please read the notes on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau 499421 A7 _B7_ V. Description of the invention (1 to 20% by mass is better, more preferably 0.1% by mass S: ~ 10% by mass S. (K inert solvent dilution) In the method for preparing the hydrogenated ester of the present invention As far as it is easy to control the hydrogenation decomposition reaction with a lower reaction temperature and the calorific value accompanying the hydrogenation (for example, with 1kg of allyl acetate hydrogenation, the calorific value is 1 607KJ), because only the esters containing unsaturated groups are reacted with Due to the heat generated by the hydrogenation, the temperature rises due to the heat generated in the reaction system, which promotes the hydrogenation decomposition reaction. In the present invention, in order to suppress the increase in the extreme temperature, the unsaturated group-containing ester is used in the hydrogenation reaction. K Diluted with inert solvents It is preferable to perform the hydrogenation reaction with the "raw material liquid" of the ester of the base. Here, the "inert solvent" means a solvent that does not substantially affect the hydrogenation reaction of the unsaturated group-containing ester of the present invention. The unsaturated group-containing ester is used. K Diluted with an inert solvent, using an unsaturated group-containing ester raw material liquid to perform the hydrogenation reaction in the form of an unsaturated group-containing ester concentration W lwtiK ~ 50wt! K is more preferred, and 3wtS is more preferred! ~ 3 0 The best wt% is 5wt! K ~ 15wt! S: If the concentration of the unsaturated group containing ester is less than 1 wt S :, it can fully suppress the extreme increase in temperature due to heat generation, but the concentration of the ester containing unsaturated group If it is too low, the productivity is reduced. In addition, if the concentration of the unsaturated group-containing ester is more than 50%, it is difficult to suppress the extreme rise in temperature due to heat generation, and it is impossible to control the adiabatic liquid phase reaction (especially In the adiabatic gas-liquid two-phase liquid-phase reaction), the temperature in the reactor (for example, the temperature of the reactor cannot be controlled to ου ~ 2〇ου) is increased. (Inert solvent in hydrogenation reaction) This paper Standards apply to Chinese National Standards (CNS) A4 specification (210 X 297 mm) Packing -------- Order -------- Disgrace (Please read the precautions on the back before filling out this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_

V. Description of the invention (I) The "inert solvent used in the hydrogenation reaction" used in the above form is not particularly limited, and an organic solvent having no C = C is preferred in terms of difficult hydrogenation reaction. This inert solvent is used by the present invention The recovery of the hydrogenated ester produced by the hydrogenation reaction does not substantially hinder the control of the hydrogenation reaction of the present invention, and there is no particular problem. In this regard, even when KC = C 鐽 is completely hydrogenated at the time of recovery, it is a saturated ester. More specific examples of the above inert solvents, such as ethyl acetate, n-propyl acetate, butyl acetate, isopropyl acetate, n-propyl propionate, ethyl propionate, butyl propionate, isopropionate Saturated esters such as propyl esters, hydrocarbons such as cyclohexane, n-hexane, and n-heptane; aromatic hydrocarbons such as benzene and toluene; ketones such as acetone and methyl ethyl ketone; carbon tetrachloride, chloroform , Halogenated hydrocarbons such as methylene chloride, methyl chloride, etc .; ethers such as diethyl ether, di-n-propane ether; ethanol, n-propanol, isopropanol, n-butanol, and 2-butanol And other alcohols; N-methyl-2-pyrrolidone, N, N-dimethylacetamide and the like Amines, etc. Among them, saturated esters, hydrocarbons, and amidines can be used in the case where they are not easily subjected to a hydrogenation reaction and do not easily cause a hydrogenolysis reaction of an unsaturated group-containing ester. (Products) According to the present invention, When the unsaturated group-containing ester is hydrogenated to M, a hydrogenation catalyst capable of controlling the hydrogenation decomposition reaction can be obtained. In addition, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-acetate can be prepared by using the catalyst. Butyl, isobutyl acetate, 2-butyl acetate, n-propyl propionate, isopropyl propionate, ethyl propionate, n-butyl propionate, isobutyl propionate, 2-butyl propionate Ester, etc. without hydrogenated saturated esters. This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) I ---------- &quot; ^ 装 -------- Order --------- ^^ 1 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_ V. Description of Invention (27) (Reaction Form) The reaction form in the production method of the hydrogenated ester of the present invention may be a gas phase reaction or a liquid phase reaction. (Gas phase reaction) First, the gas phase reaction will be described. The structure of the reaction device at the time of the reaction can be fixed layer type reaction device, mobile layer type reaction device, fluid layer type reaction device, etc. Fixed layer type reaction device is the most general. (For detailed description of this type of reaction device, please refer to Hashimoto Ken's "Reaction Engineering ", 2 GO pages ~ 2 04 pages, (stock) Peifeng Pavilion, issued in 1979). And it is better to consider the following when it is a gas phase reaction. Generally speaking, the calorific value accompanying hydrogenation is extremely large (for example With the hydrogenation of 1 fc g of allyl acetate, the calorific value is about 16 0 7 k J). In addition, in the case of a gas-phase reaction, the input temperature of the reaction substance in the reactor should be above the boiling point. At this time, the space-time When the yield is increased, the calorific value increases with hydrogenation, the temperature in the reactor rises above an appropriate reaction temperature (for example, 20 ° C), and the hydrogenation decomposition reaction is accelerated. The countermeasures include, for example, reducing the space-time yield and suppressing heat generation, or controlling the temperature by cooling or the like. When this point 傺 is a liquid phase reaction, the input temperature of the reaction substance in the reactor can be lower than the boiling point, so it can easily maintain an appropriate reaction temperature (for example, below 200 ° C). (Liquid Phase Reaction) Next, the liquid phase reaction will be described. Specific examples of the structure of the reaction device in the liquid phase reaction, such as fixed layer ~ 2 9-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) rfl ^ lklIL-— — &quot; I-IK ---- ^ 11111111 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7 _ V. Description of the invention (Ί type, flow layer type, mixing tank type, etc. Reaction device (For a detailed description of the reaction device, refer to, for example, Hashimoto Kenji's "Industrial Reaction Device-Selection, Design, Example 1", pages 4 to 34 (Peifeng Museum, issued in 1984). In terms of the ease of separation of the medium and the product, a fixed-layer type reaction device is the best among these reaction devices. The "fixed-layer type reaction device" of the present invention is a flow-through reaction device in which a catalyst is filled in a fixed layer. For example, the apparatus described in the above-mentioned document "Industrial Reaction Apparatus-Selection, Design, Example 1" on pages 4 to 7. The method for producing a hydrogenated ester of the present invention uses hydrogen gas in a liquid phase reaction using a fixed-layer reaction apparatus. The flow mode of the fluid is a two-phase flow of the liquid containing the raw material and the gas containing the hydrogen. In the case of the gas-liquid two-phase flow, the flow mode of the gas and liquid from the raw material can be divided into gas-liquid flow and gas-liquid downward flow. The present invention can be used in any of the three modes of gas flow and gas-liquid upward co-current. However, the K gas-liquid downward co-current method is optimal in terms of effectively bringing necessary hydrogen into contact with the catalyst during the reaction. In summary, the optimal reaction form in terms of suppressing hydrogenolysis and improving space-time yield is a liquid-phase reaction of gas-liquid two-phase flow, and the direction of fluid flow is gas-liquid downward co-current type. In the liquid phase reaction of gas-liquid two-phase flow, in order to suppress the hydrodecomposition reaction that causes the temperature to rise due to heat generation in the reaction system, such an inert solvent is used to dilute an unsaturated ester, and the diluted liquid is used as the reaction liquid. It is better to perform the hydrogenation reaction in the adiabatic / liquid phase reaction. The reason is that by reducing the concentration of unsaturated esters in the reaction liquid, there is no need to cool the reactor, etc. -30-This paper is applicable to China National Standard (CNS) A4 specification (210 X 297 male ） Install ------- Order --------- ^ • 1 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ V. Description of the invention (1 (reaction device) The reaction device used in the present invention is not particularly limited, but when a fixed-layer reaction device is used in a gas-liquid parallel flow reaction mode, a reactor with a cooling jacket or A multi-tubular reaction device with a cooling jacket, an adiabatic reaction device, etc. are preferred. In terms of the construction cost of the reactor or the conversion rate of unsaturated ester-containing esters, a K-athermal reaction device is preferred. (Recovery) As described above, in the present invention, it is possible to recover a considerable hydrogenated ester (especially a saturated ester) produced by a hydrogenation reaction of an unsaturated group-containing ester, if necessary. An embodiment of this collection is, for example, the procedure shown in FIG. 1. Of course, the procedure of FIG. 1 does not exceed one example of the embodiment of the present invention, and is not limited thereby. Referring to FIG. 1, the hydrogenated ester flowing out of the reactor (5) is split into the hydrogenated ester supply pipe for recovery ③ and the piping (11) for taking out the generated liquid through the general-purpose pipe 生成 of the generated liquid stream. There is no particular limitation on the flow rate ratio between the recovery and the production liquid extraction, and it can be arbitrarily determined by the desired inlet concentration of the unsaturated group-containing ester in the reactor. Therefore, when the hydrogenated ester taken out from the reactor ⑸ is recovered as an inert solvent and is not used by K, all of it can be taken out from the piping (11) for taking out the produced liquid. Alternatively, the entire hydrogenated ester taken out of the reactor ⑸ can be recovered and used. If necessary, other inert solvents may be added from the outside. (Reaction temperature) As long as the reaction temperature in the production method of the hydrogenated ester of the present invention does not violate the present invention 31-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------- --Equipment ------- Order --------- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_ V. Description of Invention (The purpose of (1) is not particularly limited. The appropriate reaction temperature in the present invention varies depending on the type of raw material, KO ~ 200 ° C is preferred, and more preferably 40 ° C ~ 150 °. If the reaction is less than At 0 t, a sufficient reaction rate cannot be obtained, and if it is more than 200 ¾, hydrogenation decomposition is easily performed. In addition, in this specification, the reaction temperature described when producing an equivalent hydrogenated ester from an unsaturated group-containing ester is defined. The temperature is anywhere in the reactor during the hydrogenation reaction. For example, in the case of an adiabatic liquid phase reaction, the temperature difference between the reactor inlet and the reactor outlet is large due to the large amount of heat generated during the hydrogenation. Any temperature to the entire outlet of the reactor. When using a heat-insulating fixed-layer reaction device in the present invention, at least the reactor inlet (the uppermost part of the catalyst layer) and the reactor outlet (the bottom of the catalyst layer) use a thermocouple thermometer as the measuring device The reaction temperature is measured. (Reaction pressure) The reaction pressure of the present invention can obtain sufficient activity even under normal pressure when it is a gas phase reaction. Therefore, it is better to implement M under normal pressure. In addition, the allyl ester is used. It is sufficient to pressurize the degree of vaporization at a temperature of 200 ° C Μ. If necessary, the reaction can be accelerated under pressurized conditions. In addition, when the liquid phase reaction is a gas-liquid two-phase flow, In order to ensure the concentration of dissolved hydrogen, it is usually better to pressurize K. As far as the hydrogen concentration in the reactor is sufficient to ensure the gas-liquid two-phase liquid phase reaction, the flow direction of the raw material gas and liquid is the gas-liquid described above. The downward co-current method is better. For gas-liquid two-phase liquid phase reaction, the reaction pressure is M0.05MPa ~ -32-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) I- --------- Installation ------- Order --------- (Please read the note on the back first Please fill out this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_ V. Description of the invention (31) lOMPa (valve pressure) is better, more preferably -0.3MPa ~ 5MPa (valve pressure). When the pressure is less than 0.05 MPa (valve pressure), the hydrogenation reaction cannot be sufficiently promoted; in addition, when the reaction pressure is greater than 10 MPa (valve pressure), the selectivity of the hydrogenation decomposition reaction becomes large. It is necessary to fully ensure the inside of the reactor. As far as the hydrogen concentration is concerned, the above-mentioned reaction mode of gas-liquid downward cocurrent flow is the best. (M allyl ester as a form of hydrogenation raw material) Allyl ester obtained by gas phase reaction using a mixed gas of alkene, oxygen and carboxylic acid in the presence of a palladium catalyst The detailed description of the aspect of the present invention of the hydrogenation raw material is to illustrate the production of allyl acetate by this method. First, a mixed gas made of propylene, oxygen, and acetic acid is passed through the gas phase directly in the presence of a palladium catalyst to produce allyl acetate, and the allyl acetate is hydrogenated to obtain n-propyl acetate. The liquid containing allyl acetate as a raw material becomes larger. ⑴When a mixed gas made of propylene, oxygen and acetic acid is passed through the gas phase in the presence of palladium to synthesize allyl acetate, the resulting reaction gas is cooled and separated into non-condensing components and condensing components to make them condensed. The reaction crude liquid was distilled to obtain allyl acetate from the top of the column. Then, the acetic acid obtained from the bottom of the column can be recovered as a raw material of allyl acetate as described below. At this time, in order to suppress the evaporation of allyl acetate in the removal of non-agglomerated components, the acetic acid can also be reduced by a scrubber as needed. ⑵The mixed gas made of propylene, oxygen and acetic acid is passed through the gas phase directly in the presence of palladium to synthesize allyl acetate. The resulting reaction product is -33-This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) -------- Order --------- ^ 9—. 499421 A7 B7 V. Description of the Invention (3 2 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The bottom tower should be in the form of a chemical polymerized C storage tower. The opposite is true. The original is the opposite, hydrogen-based Residual tops from coagulated alcohol. The determination of a good one and its propyl ester tower, but the material is distilled. Compared with the hydrogen of esters, the concentration of ester ene is required to make allyl cold. The type of the ester is formed by the acid, ene, and the substance C on the strip is based on the base containing carboxylic acid to make acid distillate. The ester is converted into an ester, such as when it is converted into a radical. c Propane, the product, the vinegar product C, C. sylvestris C. The propene condensate is bright, even the diene c is condensed, and the liquid alkene, its acid alkene, must be lowered, and the coagulation reaction is coarse. Acid co-acids, depending on the vinegar, have a reversed increase in the betting rate. Compared with the boiling vinegar that has been reacted with the boiling vinegar, the medium and the medium with the rich evidence can choose the next balance. The hydrogen acid rate is clearly selected as the level of production and production method acid acidity acidity, carboxyl, selected t% of the hair is reduced to the ester phase after the water is collected, and the carboxyl concentrated ester is pseudo externally selected low acid 1W The condensed water should be mixed with the acid of the propylene oil, and the acidity of the carboxylic acid group 反 C, which is lower than that of the carboxylic acid and the trans-ester, is reduced. Acetic acid, glutamate esters, etc., such as propylene, high carboxylic acid, active ingredients, such as vinegar phase, and propylene, and human enes, or water, water, acid, water, etc. ) Mixed alkylated esters and chromatized media point carboxylized, but crudely added with acetic acid and its normally acidic hydrogen type. Selecting the strong hydrogen to cool, it should be made with vinegar and acetone. 1 Basic Concentrated selection of acid, etc. Due to the reaction of the material, the inhibition of n = propionic acid in the ene oil of alcohol should be based on the original gas. The corresponding components in the si Ester transesterification Γ--L --- ί ---- »-pack ----- ^ ---- order --------- (Please read the notes on the back before filling (This page) This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. At 0.3wUW. Although the theoretical point of the concentration of carboxylic acid in the raw material containing allyl ester and the easiness of inducing hydrogenolysis reaction is not clear at present, based on the inventors' opinion, the M catalyst causes hydrogenation. In the decomposition reaction, the mechanism of any one of the radical cracking reaction, Sn 1 ion reaction, Sn i-type reaction or Sn 2 reaction on the catalyst is dominant, or two mechanisms on K are in parallel. At this time, based on the findings of the present inventors, when there are many carboxylic acids in the raw material containing the allyl ester, the carboxylic acid is adsorbed or bonded to the oxygen of the allyl ester, and the terminal carbon of the alkenyl group is (The carbon bound to the oxygen of the ester) The electron density between the 00 bond and the oxygen of the ester decreases, and as a result, the radical cracking reaction, the Sn i-type reaction or the Sn2 type reaction are likely to cause a large proportion of hydrogenolysis. A method for reducing the concentration of acetic acid in allyl acetate obtained by reacting oxygen and acetic acid in a gas phase in the presence of a palladium catalyst is a method of re-distilling and removing acetic acid from allyl acetate obtained by the method described above. Or a method of circulating activated alumina or activated carbon and adsorbing M to remove acetic acid and the like. (Production method of allyl ester) As the catalyst for the production of allyl ester, general palladium catalysts can be used for producing allyl ester from the corresponding gas phase of oxygen, oxygen, and carboxylic acid K. In terms of improving reactivity, it is preferable to add an alkali metal carboxylate to a palladium catalyst. Furthermore, in the production of allyl esters, K is filled with a catalyst in a suitable reactor, and the reaction pressure is from normal pressure to 3,0 MPa at 100 ° C to 300 ° C (preferably 120C to 2001C). (Valve pressure), preferably between 0 MPa and 1 · OMP a (valve pressure). The amount of carboxylic acid supplied is only the amount of the newly added allyl ester, which is equivalent to the project's medium loss. -35- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I-- — — — — — — — — — — — — — — II ^-— — — — — 1— (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 499421 A7 _B7 _ V. Description of the invention (31 The amount of the loss is better when the composition is added to the desired reaction. At this time, the composition of the source gas such as hydrogen can be widely changed, but the composition outside the explosion range is better. And, For the raw material gas, an inert gas such as nitrogen can be used, and saturated hydrocarbons such as propane can also be present. The structure of the reaction device for the production of allyl esters can use a fixed-layer reaction device and a moving layer. Type reaction device, fluidized bed type reaction device, etc. (For detailed descriptions of the reaction device, see, for example, "Reaction Engineering" by Kenji Hashimoto, pages 200 to 204, (Peifeng Museum, issued in 1979). anti- For the purification of the latter liquid, it is practically advantageous to use a fixed-layer type reaction device filled with the above-mentioned catalyst in a reaction tube having corrosion resistance (for example, a reaction tube made of SUS 3 16). The hydrolytic reaction is performed by a conventional method using an acid catalyst or an acidic ion exchange resin. Examples are described below in more detail by way of examples and comparative examples, but the present invention is not limited thereto. The conversion rate, selectivity, and yield in the examples and comparative examples are defined by the following formula. Conversion rate (%) = mole number of unsaturated group-containing esters consumed by the reaction --- Molar number selectivity of unsaturated ester-containing esters added in X 100 reactor (¾) = Molar number of hydrogenated esters or by-products produced-X 100 unsaturated ester-containing esters consumed by reaction Moore paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -3 ~ I ---------- installation -------- order ---- ----- ^ 91 (Please read the notes on the back before filling this page) 499421 A7 _B7_ V. Description of the invention (1 Yield (¾) = Molar number of the hydrogenated ester generated (please read Note 3 on the back before filling this page)-X 100 Molar number of unsaturated esters consumed by the reaction. Calculated by gas chromatography (GC). The measurement conditions at this time are as follows. (GC conditions) Machine: GC-14B (Shimadzu Scientific Co., Ltd.) Detector: Hydrogen flame ionization detector

Measurement method: internal standard method (internal standard substance: n-butyl acetate) Spray temperature: 2 2 0 C Heating condition: Hold at 40¾ for 10 minutes, then raise the temperature at K10 ° C, and hold at 1501 for 10 minutes. Using a column ·· DB-WAX (manufactured by J &amp; W), inner diameter 0.25mm, length 3 m ° Example 1 A-1 (inert solvent for Μ raw material diluted by Μ) Printed by SME Intellectual Property Bureau employee consumer cooperative The flow shown in Fig. 1 is a stainless-steel cylindrical reactor 5 (inner volume: about 130 ml) with an inner diameter of 20 mm Φ and filled with 130 ml of a loaded palladium catalyst (3 mm in diameter, two A silicon oxide carrier, a palladium content of 0.5%, a specific surface area of 300 m 2 / g, and Yeniukumken Caton (produced) are used as the catalyst filling layer 6, and the M hydrogen pressure adjusts the pressure in the reactor 5 to 2. OMPa (valve pressure). From the upper part of the reactor 5, the recovered n-propyl acetate (hydrogenated ester): allyl acetate (containing unsaturated groups) The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 499421 A7 _B7_

V. Description of the invention (I ester) = 12.9: l (wt / wt) of the mixed solution, at a temperature of 40¾, the speed of M 550ml / hr is circulated in the reactor 5 through the ester supply pipe containing unsaturated groups, And the hydrogen was passed through the reactor 5 at a rate of M18.6Hl / hr from the hydrogen supply pipe 2 (fixed layer type, gas-liquid downward co-current type). The temperature at the outlet of the reactor 5 (the bottom of the catalyst layer) was 97.51C. Further, the n-propyl acetate for dilution is taken out of the product by the procedure shown in Fig. 1 and taken out from the tube 7, and is recovered from the hydrogenated hydrogen ester supply tube 3 for recovery to the reactor 5 for use. The reaction mixture obtained from the outlet of the reactor was condensed, and analyzed by the gas chromatography method (manufactured by Shimadzu Scientific Co., Ltd., GC-14B, hydrogen flame ionizer) under the above conditions. The results obtained are shown in Table 1. ----------- Equipment -------- Order --------- (Please read the precautions on the back before filling out this page) Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Copies printed on the paper are in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 499421 __B7 V. Description of the invention (^) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 1] Kind of ester of hydrogenated ester Kind of carboxylic acid Conversion rate U) Selectivity U) Yield U) Selectivity U) Example 1A-1 Allyl acetate n-propyl acetate 99.8 99.3 99.1 0.6 Example 1A-2 Allyl acetate n-propyl acetate acetic acid 100.0 99.1 99.1 0.8 Example 1A-3 Methyl acetate isobutyl acetate 99.8 98.8 98.6 1.1 Examples 1A-4 Butyl acetate n-Butyl acetate 100.0 98.8 98.8 1.1 Example 1A -5 Allyl acetate n-propyl acetate 100.0 94.0 94.0 5.9 Example 1A-6 1,3-butadiene acetate n-butyl acetate 100.0 99.1 99.1 0.8 Example 1A-7 allyl acetate n-propyl acetate 100.0 99 · 3 99.3 0.6 Example 1B -1 Allyl acetate n-propyl acetate 100 .0 96,0 96.0 3.9 Example 1B-2 Allyl acetate n-propyl acetate 100.0 95.0 95.0 4.9 Example 1B-3 Methacrylate acetate Isobutyl acetate 100-0 93.0 93,0 6.9 Example 1B-4 Butyl acetate n-butyl acetate 100.0 93.0 93.0 6.9 Example 1B-5 Allyl acetate n-propyl acetate 100 · 0 90.3 90.0 9,9 Example 1B-6 1,3-butadiene acetate n-butyl acetate Ester Acetate 100.0 95.0 95.0 4.9 Example 1B-7 Allyl acetate n-propyl acetate 100.0 96.0 96.0 3.9 ----------- Packing ----------- Order ·· ---- --- (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7__ V. Description of the Invention (3 $ m ΙΑ-2 Loaded palladium catalyst using 130ml as hydrogenation catalyst (alumina carrier, 3mm diameter × 3mm pellets, palladium content of 0.3¾, specific surface area of 100m2 / g, Yeniuken (Carton) to replace the supported palladium catalyst used in Example IA-1 (silicon dioxide carrier, 3inm ball, palladium The amount is 0.5¾, the specific surface area is 300m 2 / g, and the Yeunyi Kem Caton Co., Ltd. is used, and the temperature in the reactor is 0.9 MPa (valve pressure) instead of the 2.0 MPa used in Example 1A-1 ( Except for the valve pressure), the ester containing unsaturated group was hydrogenated in the same manner as in Example 1A-1. The temperature at the reactor outlet (bottom of the catalyst layer) was 97.5 ° F. The reaction mixture obtained from the outlet of the reactor was condensed and analyzed using a gas chromatography (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen-fired chemical detector) under the conditions described above. The obtained results are shown in Table 1. Example 1 Α-3 Loaded ruthenium catalyst using 130ml as hydrogenation catalyst (alumina carrier, diameter 3miax, length 3mm pellets, ruthenium content 0.5¾, specific surface area 100m 2 / g, Yeniukum Karton ( )) Instead of the supported palladium catalyst used in Example 1A-1 (silicon dioxide carrier, 3mm ball, palladium content of 0.5¾, specific surface area of 300m 2 / g, Yeniukum Karton (shares) The same method as in Example 1A-1 was used except that the mixed solution of allyl acetate and n-propyl acetate used in Example 1A-1 was a mixed solution of methacrylate acetate and isobutyl acetate. The unsaturated group-containing ester is hydrogenated. The temperature at the reactor outlet (bottom of the catalyst layer) was 95.5 ° C. -40-This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ----------- installed ------- ordered -------- -(Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_ V. Description of the invention (39) The reaction mixture obtained from the reactor outlet is condensed and a gas chromatography analyzer is used (Shimadzu Scientific Co., Ltd., GC-14B, Hydrogen Ionization Detector), M Analysis of the above conditions. The results obtained are shown in Table 1. Example 1 A-4 Loaded rhenium catalyst using 130ml as catalyst (alumina carrier, diameter 3mm × length 3mm pellets, rhodium content 0.5¾, specific surface area 100m 2 / g, Yeniukum Karton (stock )) Instead of the supported palladium catalyst used in Example 1A-1 (silicon dioxide carrier, 3mm diameter ball, palladium content of 0.5¾, specific surface area of 300m 2 / g, Yenuyi Kemton (stock) system ), And the temperature in the reactor was set to 0.9 MPa (valve pressure) to replace the mixture of allyl acetate and n-propyl acetate in the raw materials used in Example 1A-1, each of which was butenyl acetate and n-butyl acetate. Except for the ester mixture, M was hydrogenated in the same manner as in Example 1A-1. The temperature at the reactor outlet (bottom of the catalyst layer) was 95.5 ° C. The reaction mixture obtained from the reactor outlet was condensed and analyzed using a gas chromatography (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) under the conditions described above. The results obtained are shown in Table 1. Example 1 Α-5 Use 130ml as a catalyst to load nickel catalyst (1Π content 70%, A1 content 30¾, trade name; R-222L, Niorica (transliteration) (stock) system) to replace the example 1A-1 supported palladium catalyst (silicon dioxide carrier, 3mm diameter ball, palladium content of 0.5¾, specific surface area of 300m2 / g, manufactured by Yeniukum Karton Co., Ltd.), and a reactor The internal temperature is 0.9 MPa (valve pressure) instead of the 2.0 MPa (valve pressure) used in Example 1A-1, and M and Example -41- This paper size applies to China National Standard (CNS) A4 (210 X 297) Mm) ---------------------------- (Please read the notes on the back before filling out this page) Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative 499421 A7 B7__ 5. Description of the invention (40) 1A-1 The same method is used to hydrogenate unsaturated esters. The temperature at the reactor outlet (bottom of the catalyst layer) was 97.5 ° C. The reaction mixture obtained from the outlet of the reactor was condensed and analyzed using a gas chromatography (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen-fired chemical detector) under the conditions described above. The results obtained are shown in Table 1. Example ... lA-il .. Loaded palladium catalyst using 130ml as catalyst (alumina carrier, diameter 3mmx length 3mm pellets, rhenium content 0.5¾, specific surface area 100m2 / g, Yeniukum Karton (Manufactured by the company) to replace the supported palladium catalyst used in Example 1A-1 (silicon dioxide carrier, diameter 3mm ball, palladium content 0.55¾, specific surface area 300m 2 / g, Yeniukum Karton ( )), And K 1,3-butadiene acetate: n-butyl acetate = 30: 1 Ut / wt) instead of allyl acetate: n-propyl acetate = 12.9: l (wt Except for the mixture in wt.%, the unsaturated group-containing ester was hydrogenated in the same manner as in Example 1A-1. The temperature at the reactor outlet (bottom of the catalyst layer) was 105¾. The reaction mixture obtained from the reactor outlet was condensed and analyzed using a gas chromatography (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) under the conditions described above. The results obtained are shown in Table 1. Example 1 Α-7 (manufactured by hydrogenated catalyst rhenium) 1.66 g of Na2PdCl4 (manufactured by Tanaka Takagami Chemical Industry Co., Ltd.) (aqueous solution A) dissolved in 80 ml of water was introduced into a 1JI flask. 200 g of 7-alumina ball (made by Nippon Unabasaru, trade name {^ 1 ^ 3; acid point 5.6 \ 103), average diameter-42-sheet Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm). ------------------------------- Order (please read the precautions on the back first) (Fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_ V. Description of the invention (M 3.2mm, specific surface area 165m2 / g, full pore volume 0.90ml / g), so that the total amount of aqueous solution A is absorbed at -Alumina. Measure 2.63g of Na2Si03 and 9H20 into different beakers, add 100g of water to M to dissolve, and prepare aqueous solution B. In a flask to prepare the aqueous solution B, add the aqueous solution A-7 that absorbs the above obtained- Alumina was allowed to stand at room temperature for 20 hours. Then, 12.9 g of trap 1 hydrate was added at room temperature with K stirring. After adding trap 1 hydrate, it was stirred for another 4 hours. Filter the funnel to separate the catalyst, and use a glass container that can pass water. Through this catalyst, the flow rate of K is about 60ml / min. 48 After pure water, it was dried for 4 hours under an air stream and ηου to prepare a hydrogenated catalyst ⑴. When the acid point of the hydrogenated catalyst 如此 thus obtained was analyzed by the ammonium-TPD method described below, the acid point was 1.1X1 ( Γ3 millimolars / g. The measurement conditions of the ammonium-TP D method used here are described in the following. Measuring equipment: Automatic temperature rise and separation analysis device (vacuum exhaust type) (Ben Beru (transliteration) (stock) Preparation of the measurement sample: Use whey to finely pulverize the sample. Measure 90 ng of the finely pulverized sample and use the ammonium-TPD measurement sample. Temperature rising conditions · The above-mentioned automatic temperature rise is separated from the analysis device, so that After the sample was dried at 200 ° C for 60 minutes, the M-IOC / minute was cooled to 100 ° C, and then the ammonium was adsorbed for 1 hour at 100 ° C. The temperature was raised to 600 ° C and kept directly for 10 minutes. Calculate the acid point: In the temperature range of 2301 ~ 6001C, use a mass spectrometer to obtain the number of molecules of ammonium detached from the sample. Make the number of ammonium -43- This paper standard applies Chinese National Standard (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back first (Write this page) -------- Order --- 499421 A7 B7_ V. Description of the invention (1 The number of molecules is divided by the amount of sample used to calculate the acid point. (Manufacture of hydrogenated esters) (please first Read the notes on the back and fill in this page again.) Use 130ml of the hydrogenated catalyst manufactured above as the catalyst. 0) Instead of the supported palladium catalyst (silicon dioxide carrier, 3mm diameter ball) used in Example 1A-1. , Palladium content of 0.5¾, specific surface area of 300m 2 / g, manufactured by Yeniukumken Caton Co., Ltd., and the hydrogen flow rate was 37.2Jl / hr to replace the 18.6A / hr used in Example 1A-1. In the same manner as in Example 1A-1, the unsaturated group-containing ester was hydrogenated. The temperature at the reactor outlet (bottom of the catalyst layer) was 9 4 ° C. The reaction mixture obtained from the outlet of the reactor was condensed and analyzed using a gas chromatography (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen-fired chemical detector) under the conditions described above. The results obtained are shown in Table 1. Example 1B-1 (Undiluted ester containing unsaturated group) Printed clothing of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Printed in a stainless steel cylindrical reactor with an inner diameter of 20 μm tube sleeve was filled with 130ml and Example 1A- 1. The same supported palladium catalyst is used, and the sleeve temperature is set to 90¾, the pressure M in the reactor is adjusted to 2.0MPa (valve pressure), and allyl acetate is made from the upper part of the reactor. At a flow rate of 300 ml / hr at 100 ¾, hydrogen was passed at a rate of 8.6 Jl / hr, and the ester containing an unsaturated group was hydrogenated. The temperature at the reactor outlet (bottom of the catalyst layer) was 102 ° C. The reaction mixture obtained from the reactor outlet was condensed and analyzed using a gas chromatography (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) under the conditions described above. The obtained results are shown in Table 1. 44- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 499421 A7 B7 Printed by the Consumer Finance Cooperative of the Smart Finance and Economics Bureau of the Ministry of Economic Affairs 1 B-2 Except that the catalyst is the same and the response is the same In order that the reactor comes from the reaction analyzer (in the above example 1 B-3 except that the catalyst is the same, M and the reactor comes from the reaction analyzer (M in the above example ί 1 Β-4 except that the catalyst is the same, Instead of the reactor used in Example 1 A-1, the reactor used was from the reaction analyzer (5. Description of the invention ("1 3 0 m 1 and the catalyst used in Example 1 A-2 as the catalyst). The pressure in the device with the same negative palladium catalyst is 2.0 MPa (valve pressure) to 0.9 MPa (valve pressure). Example 1 B-1 The hydrogenated ester containing unsaturated group is hydrogenated in the same way. Mouth (bottom of catalyst layer) The temperature was 10210. The reaction mixture obtained at the outlet of the reactor was condensed and analyzed using conditions of Shimadzu Scientific Co., Ltd., GC-14B, hydrogen flame ionization detector. The results are shown in Table 1. 130ml and The catalyst used in Example 1A-3 was to replace Example 1 A-1 The same supported palladium catalyst was used in the same way as in Example 1 B -1. The unsaturated ester-containing ester was hydrogenated. The temperature at the mouth (the bottom of the catalyst layer) was 102 ". The reaction mixture obtained at the outlet of the reactor was condensed and used. Gas chromatography Shimadzu Scientific Co., Ltd., GC-14B, argon flame ionization detector). The results are shown in Table 1. 430 ml was used as the catalyst in Example 1A-4. The negative type is used instead of the supported palladium catalyst used in Example 1A-1. The same method as in Example 1 B -1 is used to hydrogenate the unsaturated ester-containing ester. The temperature of the mouth (the bottom of the catalyst layer) is 102. It. The reaction mixture obtained at the outlet of the reactor is condensed, using Shimadzu Scientific Co., Ltd., gas chromatography GC-14B, hydrogen fire ionization detector) -45 This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) --- ^ -------- install ------ r (Please read the precautions on the back before filling out this page) Order --------- Wisdom of the Ministry of Economic Affairs Printed by the Consumer Affairs Cooperative of the Property Bureau 499421 A7 B7_ 5. Description of the invention (, K Analysis of the above conditions. The results are shown in Table 1. Example 1 B-5 Except for use 130ml is the same as the loaded nickel catalyst used in Example 1A-5 as the catalyst, replacing the same loaded palladium catalyst used in Example 1A-1, and the pressure in the reactor is 2.0MPa ( Valve pressure) to 0.9 MPa (valve pressure). The unsaturated group-containing ester was hydrogenated in the same manner as in Example 1B-1. The temperature at the reactor outlet (the bottom of the catalyst layer) was 102 ° C. The reaction mixture obtained from the reactor outlet was condensed and analyzed using a gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) under the conditions described above. The results obtained are shown in Table 1. Example 1 B-6 except that 130 ml of the same loaded palladium catalyst used in Example 1A-6 as the catalyst was used instead of the same loaded palladium catalyst used in Example 1A-1, and used as 1,3-butadiene acetate: n-butyl acetate = 2Θ s 18 (wt / wt) was used as the raw material mixture to replace the allyl acetate: n-propyl acetate used in Example 1 A-1 Except for 12.9: 1 Ut / wt), the same procedure as in Example 1B-1 was used to make the ester containing unsaturated group hydrogenate. The temperature at the reactor outlet (bottom of the catalyst layer) was 102 1C. The reaction mixture obtained from the reactor outlet was condensed and analyzed using a gas chromatography (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) under the conditions described above. The results obtained are shown in Table 1. Example 1 Β-7 except that the same hydrogenated catalyst used in Example 1A-7 as 130ηι1 was used instead of the same supported palladium catalyst used in Example 1 A-1, 46-this Paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm), --- II * ---: ------------------------------------- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ V. Description of the invention (1 and make the hydrogen flow rate 37.2 A / hr instead of Example 1 The ester containing unsaturated group was hydrogenated in the same manner as in Example 1 B-1 except for 18.6 il / hr used in A-1. The temperature at the outlet of the reactor (the bottom of the catalyst layer) was 102. 〇C. The reaction mixture obtained from the outlet of the reactor was condensed and analyzed using a gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) under the conditions described above. The results obtained are shown in the table. Shown as 1. Compare the above-mentioned Example 1 A-1 and Example 1B-1, Example 1 A-2 and Example 1B-2, Example 1A-3 and Example 1B-3, Example 1A-4 and Example 1B- 4.Examples 1A-5 and 1B-5, Examples 1A-6 and 1B- 6. In the case of Examples 1 A-7 and 1B-7, it can be known that by diluting the unsaturated group-containing ester in the form of the present invention with an M inert solvent, a hydrogenated ester having no accompanying hydrolytic decomposition reaction can be produced at a high yield. Example 2A-1 (manufactured by hydrogenation catalyst) 1.66 g of Na2PdCl4 (manufactured by Tanaka Precious Metals Industry Co., Ltd.) (aqueous solution A) previously dissolved in 190 ml of water was introduced into a 1JI flask. 200 g of silica balls were added to the flask. (Fuji Silesia (transliteration) chemical (stock), trade name Cariact Q-10; acid point 1.1X10_3 millimoles / g, average diameter 3nim, specific surface area 300m2 / g, full pore volume 1.0 ml / g), The entire amount of the aqueous solution A was absorbed in silicon dioxide. 2.63 g of Na2Si03 and 9H2O were each placed in different beakers, and 100 g of water was added to the solution to dissolve M to prepare an aqueous solution B. Into a flask prepared with the aqueous solution B was added Absorb the silicon dioxide of the aqueous solution A obtained above, and leave it to stand at room temperature for 20 hours. After adding hydrazone-1 hydrate, in addition -47- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling in this ) A ^^ 1 ^^ 1 1 I · ϋ 1_ one, I m mmmt ϋ ^ 1 · ^ 1 »I - Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives printed 499421 A7 _B7_ V. description of the invention (1 for 4 hours. The catalyst was separated by filtering using a funnel, and a water-permeable glass container was used. Through the catalyst, a flow rate of about 60 m 1 / min was used to circulate pure water for 48 hours. It was then dried for 4 hours to prepare hydrogenated catalyst rhenium. When the acid point K of the hydrogenation catalyst ⑵ thus obtained was analyzed by the ammonium-TPD method described below, the acid point was 1.1 X 1 (Γ3 mmol / g. Example 2 A-2 (Hydrogenation Catalyst (3) (Production) 1.66 g of Na2PdCl4 (manufactured by Tanaka Precious Metals Co., Ltd.) (aqueous solution A) dissolved in 80 ml of water was introduced into an IA flask. 200 g of 7-alumina ball (Nippon Unabasaru (transliteration) ), Trade name NST-3; acid point 5.6X103 millimoles / g, average diameter 3.2mm, specific surface area 165m2 / g, total pore volume 0.90nil / g), so that the entire amount of aqueous solution A is absorbed in 7-oxidation Aluminum. Measure 2.63g of Na2Si03 and 9H2O into different beakers, add 100g of water to M to dissolve, and prepare aqueous solution B. In a flask to prepare this aqueous solution B, add 7-7 which absorbs the obtained aqueous solution A above- Alumina was allowed to stand at room temperature for 20 hours. Then, 12.9 g of trap 1 hydrate was added at room temperature with stirring. After adding tritium 1 hydrate, it was stirred for another 4 hours. The catalyst is separated by filtering through a funnel, and a glass container that can pass water is used. Through the catalyst, M is about 60rol / min. After flowing pure water for 48 hours, it was dried for 4 hours under an air current of 110 ¾ to obtain a hydrogenation catalyst ③. The acid point M of the hydrogenation catalyst ③ thus obtained was the same as in Example 2 A -1. -This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----------- installation -------- order --------- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed on 499421 A7 B7_ V. Description of the invention (When the conditions and methods are analyzed by the ammonium-TPD method, the acid point is 5.6 ΧΙΟ-3 millimoles / g. M 2 A-3 (manufactured by hydrogenation catalyst) 2.765 g of Na2PdCl4 (manufactured by Tanaka Precious Metals Industry Co., Ltd.) (aqueous solution A) dissolved in 90 ml of water was introduced into a 1JI flask. This flask was charged with 200 g of 7-alumina spheres (trade name: KHA-24; manufactured by Sumitomo Chemical Co., Ltd .; acid point: 1.0X1 0-2 mmol / g) to absorb the entire amount of aqueous solution A into 7-alumina. Measure 4.38g of Na2Si03 and 9H20 into different beakers, add 100g of water to M to dissolve, and prepare aqueous solution B. Add the absorption to the flask that prepared the aqueous solution B The alumina of the obtained aqueous solution A was allowed to stand at room temperature for 20 hours. Then, 12.9 g of 胼 1 hydrate was added at room temperature with stirring. After adding 胼 1 hydrate, the mixture was stirred for 4 hours. The catalyst was separated by filtration, and the catalyst was washed 10 times with 1% pure water, and then dried under the conditions of 70 °, 10111111 {^ (11111111 ^ = 1 33.322?). Then in a hydrogen atmosphere at 2001C for 2 hours (conditions for reduction treatment; pressure IMPa (valve pressure), hydrogen flow rate 18.6 N1 / h r &gt;), hydrogenated catalyst rhenium was prepared. When the acid point K of the hydrogenated catalyst rhenium thus obtained was measured under the same measurement conditions and method as in Example 2A-1 by the ammonium-TPD method, the acid point was 1.0 × 10_2 millimoles / g. Example 2 A-4 (manufactured by hydrogenated catalyst) -49- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ----------- pack --- ----- Order --------- (Please read the notes on the back before filling this page) 499421 A7 B7_ 48 V. Description of the invention () (Please read the notes on the back before filling this page ) 2.54 g of RhCl 3 · 3H 2 0 (made by Wako Pure Chemical Industries, Ltd.) (aqueous solution A) previously dissolved in 190 ml of water was introduced into a 1-liter flask. Into this flask was added 200 g of silica dioxide balls (Cariact Q-10 manufactured by Fuji Silica Chemical Co., Ltd .; acid point 1.1 × 1 (Γ3 mmol / g, average diameter 3 mm, specific surface area 300 m 2 / g, full fineness). The pore volume is 1.0 ml / g), so that the entire amount of the aqueous solution A is absorbed in the silicon dioxide. 6.79 g of Na2Si03 and 9H20 are measured and placed in different beakers, and 100 g of water is added to K to dissolve, and the aqueous solution B is prepared. Into the flask for preparing the aqueous solution B, the silica dioxide absorbing the above-obtained aqueous solution A was added and left at room temperature for 20 hours. Then, the contact was separated by filtration, and the contact was made with pure water scorching M 1JI. After the medium was washed 10 times, it was dried under the conditions of 701 and 10 mmHg. Then, under a hydrogen atmosphere, 200 t: Sugawara treatment for 2 hours, (conditions of relocation treatment; pressure IMPa (valve pressure), hydrogen flow rate 18 6 N 1 / hr) to prepare a hydrogenated catalyst ⑸. When the acid point M of the hydrogenated catalyst ⑸ thus obtained was the same as in Example 2A-1, the measurement conditions and methods were analyzed by the ammonium-TPD method. 1.0 × 10-3 millimoles / g. Example 2 A-5 (manufacturing of hydrogenation catalyst (6)) Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Shosha Co., Ltd. introduced 2.41 g of RuC13, nH2 0 (n = 1-3) (made by Wako Pure Chemical Industries, Ltd.) (aqueous solution A) previously dissolved in 80 ml of water into a ljl flask. 200 g of 7 was added to the flask. -Alumina ball (manufactured by Nippon Sasar) and trade name NST-3; acid point 5.6X10_3 millimoles / g, average diameter 3.21 «111, specific surface area 1651112 / ^, full pore volume 0.9. 1 «1, -50-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 499421 A7 B7_ 5. Description of the invention (", so that the entire amount of aqueous solution A is absorbed in 7-alumina. Please read the precautions on the back before filling this page.) Measure 6.91g of Na2Si〇3, 9H2O into different beakers, add 100g of water to dissolve, and prepare aqueous solution B. Add to the flask that prepared the aqueous solution B. The 7-alumina of the aqueous solution A obtained above was absorbed and allowed to stand at room temperature for 5 hours. Then, 12.9 g of hydrazone-1 hydrate was slowly added to the mixture with stirring at room temperature. Trap 1 hydrate was added. After that, stir for another 4 hours, and then separate the contacts by filtering with a hopper funnel. A water-permeable glass container was used. After passing the catalyst, a flow rate of K of about 60 ml / min was passed for 48 hours, and then dried under an air stream of 110 for 4 hours to prepare a hydrogenated catalyst (6). 0X10-3 mmol / g。 The acid point M of the hydrogenation catalyst ⑥ thus obtained was measured under the same conditions and methods as in Example 2A-1 when analyzed by the ammonium-TPD method. Example 2 A-6 (Production of hydrogenated esters) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, referring to Figure 1, a cylindrical reactor made of stainless steel with an inner diameter of 20 μm is filled with 130 ml of the hydrogenated catalyst produced in Example 2A-1 The pressure M in the reactor was adjusted to 2.0 MPa (valve pressure). From the upper part of the reactor, the recovered mixture of n-propyl acetate: allyl acetate = 12.9: 1 Ut / wt) was flowed at a rate of 550 ml / hr at 40 ° C, and hydrogen was flowed at a rate of W 18.6 Nl / hr. Inside the reactor. The temperature at the reactor outlet (bottom of the catalyst layer) was 9 4 C. The reaction mixture obtained from the outlet of the reactor was condensed. A gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization) was used to pick out the paper. The standard of this paper is Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_

V. Description of the invention (I device) K As a result of the above-mentioned condition analysis, the conversion rate of allyl acetate is 99.8¾, the selectivity of n-propyl acetate is 99.3¾, and the yield of n-propyl acetate is 99.1¾, and The selectivity of acetic acid is 0.6 »:. Example 2 A-7 (Production of hydrogenated ester) Except the use of 130rol and the hydrogenated catalyst produced in Example 2A-2 as a catalyst to replace the hydrogenated catalyst produced in Example 2A-1, and the pressure in the reactor Instead of the 2.0 MPa (valve pressure) used in Example 2A-6, the pressure was 0,9 MPa (valve pressure). The unsaturated group-containing ester was hydrogenated in the same manner as in Example 2A-6. The temperature at the reactor outlet (bottom of the catalyst layer) was 9410. The reaction mixture obtained from the outlet of the reactor was condensed, and a gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) was used. The results of the analysis under the conditions described above, the conversion of allyl acetate The rate was 100.0%, the selectivity of n-propyl acetate was 98.6¾, the yield of n-propyl acetate was 98.6%, and the selectivity of acetic acid was 1.3¾. Example 2 A-8 except that 130 ml of the hydrogenated catalyst (6) produced in Example 2A-5 was used instead of 130 ml of the hydrogenated catalyst produced in Example 2A-1. The ester is hydrogenated. The temperature at the reactor outlet (bottom of the catalyst layer) was 9 4 t. The reaction mixture obtained from the reactor outlet was condensed, and a gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) was used. K As a result of the above-mentioned condition analysis, the conversion of allyl acetate The rate is 99.8¾, the selectivity of n-propyl acetate is 98.8¾, and the yield of n-propyl acetate is 52.-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) I --- ------- Installation -------- Order --------- (Please read the precautions on the back before filling out this page) Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ 5. Description of the invention (Ί 98.6%, and the selectivity of acetic acid is 1.1¾. Example 2 A-9 (manufactured by hydrogenated ester) Except the use of 130inl and hydrogenated catalyst produced by Example 2A-4 as catalyst ⑸ Instead of the hydrogenation catalyst produced in Example 2A-1, the same method as in Example 1B-1 was used to hydrogenate the unsaturated ester-containing ester. The temperature at the reactor outlet (the bottom of the catalyst layer) was 9 4 C. The reaction mixture obtained from the outlet of the reactor was condensed, and a gas chromatograph (manufactured by Shimadzu Scientific Co., Ltd., GC-14B, hydrogen flame ionization detection) was used. According to the above conditions, the conversion rate of allyl acetate was 100.0¾, the selectivity of n-propyl acetate was 98.8¾, the yield of n-propyl acetate was 98.8¾, and the selectivity of acetic acid was 1.1. %. Example 2 A-10 (Production of hydrogenated ester) Referring to FIG. 1, a cylindrical reactor made of stainless steel with an inner diameter of 20 min4 was filled with 130 ml of hydrogenated catalyst 触 manufactured in Example 2A-3, and the inside of the reactor was filled. The sleeve temperature was set to 90.〇υ, and the pressure was adjusted to 2.0 MPa (valve pressure) with hydrogen. Allyl acetate was passed from the upper part of the reactor at a speed of 300 ml / hr at a rate of 300 ml / hr, and the hydrogen was K 1 8 6 N 1 / hr flow through the reactor. The temperature at the reactor outlet (bottom of the catalyst layer) is 90.5 ° C. The reaction mixture obtained from the reactor outlet is condensed and a gas chromatography analyzer (Shimadzu Science) is used. (Product), GC-14B, hydrogen fire ionization detector) As a result of analysis under the above conditions, the conversion rate of allyl acetate was 100.0%, the selectivity of n-propyl acetate was 98.0%, acetic acid One of n-propyl ester 53-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I ---------- install ------- order --------- ^ 9 (Please read the phonetic on the back? Matters before filling out this page) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the employee consumer cooperative 499421 A7 B7_ V. Description of the invention ("The yield is 98.0¾, and the selectivity of acetic acid is 1.9%. Example 2 A-1 1 (Manufacture of hydrogenated ester) 130ml of hydrogenation manufactured in Example 2A-2 Catalyst (3) was used to replace the hydrogenated catalyst ⑵ manufactured in Example 2 A-1 in 130m, and a mixture of S§ acid 1, 3-butadiene ester and n-butyl acetate was used instead of the catalyst used in Example 2A-6. Allyl acetate and n-propyl acetate constituting the mixed liquid of the raw materials, and the flow rate of hydrogen K 37.2! <1 / ^ is used instead of 18.6 «1 / ^ 1" used in Example 2 & -6. The same method M as in Example 2 A-6 was used to hydrogenate the unsaturated group-containing ester. The temperature at the reactor outlet (bottom of the catalyst layer) was 95.5 ° C. The reaction mixture obtained from the reactor outlet was condensed, and a gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) was used. K The result of the above-mentioned analysis, acetic acid 1,3- The conversion of butadiene ester was 100.0¾, the selectivity of n-butyl acetate was 99.1¾, the yield of n-butyl acetate was 99.1¾, and the selectivity of acetic acid was 0.9¾. Example 2 B-1 (Production of hydrogenated ester) Referring to Fig. 1, a stainless steel cylindrical reactor with an inner diameter of 20 mm was filled with 130 ml of an acid point of the ammonium-TPD method measured under the same measurement conditions as in Example 2A-6. 2.0 X 1 (T1 millimolar / g sponge nickel catalyst (Ni content 70%, A1 content 30¾, made by Niorica, stock name, R-200L), and The pressure was adjusted to 0.9 MPa (valve pressure) with hydrogen. From the upper part of the reactor, the recovered mixed liquid of n-propyl acetate: allyl acetate = 12.9: 1 (wt / wt) was 550 M / hr at 401. Speed, and make the first 54-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I --------- i I I ---- Order ---- --- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 __B7_ V. Description of the invention (53) Μ 18.6Nl / hr circulates in the reactor. Reactor The temperature at the outlet (the bottom of the catalyst layer) was 95.5 ° C. The reaction mixture obtained from the reactor outlet was condensed, and a gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen fire ion) was used. Chemical detector) As a result of analysis under the above conditions, the conversion rate of allyl acetate was 100,0¾, the selectivity of n-propyl acetate was 94.0¾, the yield of n-propyl acetate was 94.0¾, and The selectivity was 5.9¾. Example 2B-2 (Production of hydrogenated ester) Referring to the first figure, a stainless steel cylindrical reactor with an inner diameter of 20 mm 0 was filled with 130 ml of ammonium measured under the same measurement conditions as in Example 2A-6. -TPD method with a loaded palladium catalyst with an acid point of 2.0X10 millimolars / g (alumina support, palladium content of 5¾, made by Tanaka Precious Metals Co., Ltd.), and setting the casing temperature to 90.01, The pressure was adjusted to 2 * © MPa (valve pressure) with hydrogen. From the upper part of the reactor, allyl acetate was passed at a rate of 300 ml / hr at 401 M, and hydrogen was passed through the reactor at a rate of M18.6 Nl / hr. The temperature at the reactor outlet (the bottom of the catalyst layer) was 90.5 ° C. The reaction mixture obtained from the reactor outlet was condensed, and a gas chromatography analyzer (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen fire) was used. Detector) As a result of the above-mentioned condition analysis, the conversion of allyl acetate was 100.0¾, The selectivity of propyl ester is 92.0¾, the yield of n-propyl acetate is 92.0¾, and the selectivity of acetic acid is 7.9¾. Example 2B-3 (manufactured by hydrogenated esters) -55-This paper size applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) ------------------- Order ---------- (Please read the precautions on the back first (Fill in this page) 499421 A7 B7_ V. Description of the invention (54) (Please read the precautions on the back before filling in this page) Refer to Figure 1 and fill in a stainless steel cylindrical reactor with an inner diameter of 20mm0. 1 3 0 m 1 measured by the same measurement conditions as in Example 2 A-6? 0 method acid point 2,0 \ 10_1 millimoles / 8 of sponge nickel catalyst ({&1; content 7 (U, A1 content 30¾, Niorica (stock) system, product name R-200L) And the pressure K in the reactor was adjusted to 0.9 MPa (valve pressure). From the upper part of the reactor, n-butyl acetate recovered: 1,3-butadiene acetate = 12.9: 1 Ut / wt) The mixed liquid was at a rate of M 550 ml / hr at 40 ¾, and hydrogen was allowed to flow in the reactor at a rate of 37.2 Nl / hr. The temperature at the reactor outlet (bottom of the catalyst layer) was 9 5 · 5 ° C. The reaction mixture obtained from the reactor outlet was condensed, and a gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) was used to analyze the results under the conditions described above. Acetic acid 1,3- The conversion of succinate was 100.0¾, the selectivity of n-butyl acetate was 94.0¾, the yield of n-butyl acetate was 94.0¾, and the selectivity of acetic acid was 5.9¾. m 3A-1 (Production of allyl esters) Μ Impregnation method loads 45g of palladium and 52g of potassium acetate on 540g of silicon dioxide (surface area 96m 2 / g, pore volume 0.78inl / g, average pore radius 115nm, Bulk density is 540g / l), and a catalyst with a particle diameter of 5mm is prepared. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the 1JI catalyst thus obtained was filled in a stainless steel reactor with a diameter of 27mni, and the gas composition was adjusted to 12 mol 5K propylene, 7.5 mol% oxygen, 9.0 mol Acetic acid, 71.5 moles of diluted gas, and the above catalyst heated at 145 ° C were supplied at a space velocity of 18 00 / hr, with a K reaction pressure of 0.4 MPa (valve pressure) for K reaction. 56_ This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_ V. Description of the invention (^ The resulting reaction gas is cooled and separated into The non-condensing component and the condensing component are used to distill the reaction crude liquid, and the following composition (hereinafter referred to as "composition A") is prepared from the top of the column. <Composition A &gt; Dipropyl Acetate 97.7wt $ Dilute Propanol O.lwt% acetic acid 2.0wU other 0.2wt% 5,000 ml of activated alumina (made by Tomita Pharmaceutical Co., Ltd., trade name: Dunmita A61) was filled in a glass reactor with a diameter of 10Qrmo, and the K space velocity was 1 / hr (that is, 500 in 1 / hr) was passed through Composition A to prepare a mixture of the following composition (hereinafter referred to as "composition B"). <Composition B &gt;

Allyl acetate 99.6wt% Allyl alcohol O.lwU Acetic acid O.lwt% Other 0.2wt% <hydrogenation of esters containing unsaturated groups> Refer to the first figure, a stainless steel cylinder with a sleeve inside diameter of 20 μm Type reactor was filled with 130ml of supported platinum catalyst (alumina carrier, diameter 3mmX length 3πιm pellets, platinum content 0.3¾, specific surface area 100m 2 / g, made by Yeniukum Karton (stock)), and The temperature of the sleeve was set to 90.0¾, so that the pressure in the reactor was adjusted to i · © MPa (valve pressure) with hydrogen. From the upper part of the reactor, 10 kg of the composition B was allowed to flow at a speed of 550 ml / hr at a temperature of 425 ml, and hydrogen was allowed to flow through the reactor at a speed of 18.6 Nl / hr. The temperature at the reactor outlet (bottom of the catalyst layer) was 90.5 ° C. The reaction mixture obtained from the outlet of the reactor was condensed to obtain 10 kg of a liquid. Make the liquid K have the above conditions (but the injection temperature is 200 ° C), -57-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- • Packing -------- Order --------- i (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7_ V. Description of the invention (Using a gas chromatography analyzer (Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector)) As a result of the above-mentioned condition analysis, the conversion rate of allyl acetate was 100.0¾, n-propyl acetate The selectivity of ester was 99.2%, the yield of n-propyl acetate was 99.2¾, and the selectivity of acetic acid was 0.7¾. Example 3 A-2 (Production of Allyl Ester) K impregnation method made 45g of palladium and 52g Potassium acetate was loaded on 540 g of silicon dioxide (surface area of 96 m 2 / g, pore volume of 0.78 ml / g, average pore radius of 115 nm, and bulk density of 540 g / l) to prepare a catalyst having a particle diameter of 5 mm. The catalyst was filled in a stainless steel reactor with a diameter of 27 μm, and the gas composition was adjusted to 12 mol 5K propylene, 7.5 mol% oxygen, 9.0 mol acetic acid, 71.5 Ear "; dilute the gas, and supply the W space velocity of 1 800 / hr on the above catalyst heated at 145¾, and the reaction pressure is 0.4 MPa (valve pressure) to react. This is to prepare the reaction of M allyl acetate as the main component Generate gas. Separate the resulting reaction gas into non-condensing components and condensing components. Add about 1: 1 volume ratio of water to the condensing components and use 500 ml of acidic ion exchange resin (Mitsubishi) as shown in Figure 2. Manufactured by Chemical Co., Ltd., trade name: King Laiya (Transliteration) SK-104H), circulated at a space velocity of Μ / hr (500 η 1 / hr). As a result, a portion of allyl acetate was converted to allyl Alcohol, and after the hydrolytic reaction, the reaction crude liquid is distilled to obtain a composition of K allyl alcohol, allyl acetate and water as the main components from the top of the tower. Ester and water as the main component group 5 8-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- pack ------- -Order --------- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4994 21 A7 _B7___ V. Description of the invention (The product is cooled to separate the oil phase from the water phase, and the following composition (hereinafter referred to as "composition C") is prepared from the oil phase. <Composition C &gt;

Allyl acetate 97.1tfU Allyl alcohol 0.5wU Acetic acid 2.0wU Moisture 0.2 Other 0.2% by weight 50 0ml of activated alumina (made by Tomita Pharmaceutical Co., Ltd., trade name: Dunmita A61) is filled with a diameter 100 臓 glass reactor, and the composition C of the upper 使 was circulated at a space velocity of 1 / hr (that is, 500 ro 1 / hr) to prepare a mixture of the following composition (hereinafter referred to as "composition D" "). <Composition D> Allyl acetate 99.2tft% allyl alcohol 0.4wt% acetic acid 0.2wU moisture O.lwt%

Other 0.1 wU <hydrogenation of allyl esters> Referring to the first figure, a cylindrical reactor made of stainless steel with an inner diameter of 20 mm and a sleeve was filled with 130 ml of a supported type catalyst (alumina carrier, diameter 3mmX length 3mm pellets, rhodium content of 0.5¾, specific surface area of 100m 2 / g, made by Yeniu Kem Caton (strand), and the sleeve temperature was set to 90 °, so that the pressure in the reactor was adjusted to hydrogen It is l.OMPa (valve pressure). From the upper part of the reactor, 10 kg of the composition D obtained as described above was passed at a rate of M 550 ml / hr at 40 ° C, and hydrogen was passed through the reactor at a rate of 18.6 Nl / hr. The temperature at the reactor outlet (bottom of the catalyst layer) was 90.5 ° C. -5 9-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Packing -------- Order --------- (Please read the precautions on the back first Refill this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7_ V. Description of the invention (condensation of the reaction mixture obtained from the reactor outlet to produce 10 kg of liquid. Make the liquid from the above conditions (but The spray temperature was 2001). The results were analyzed by gas chromatography. The conversion rate of allyl acetate was 100.0¾, the selectivity of n-propyl acetate was 99.1%, and the yield of n-propyl acetate was 99.1¾. And the selectivity of acetic acid is 0.8¾. Example 3A-3 Referring to the first figure, a stainless steel cylindrical reactor with an inner diameter of 20 mm and a sleeve is filled with 130 ml of a supported ruthenium catalyst (alumina carrier, diameter 3 mmX 3mm length pellets, ruthenium content of 0.5¾, specific surface area of 100ra2 / g, manufactured by Yanu Yikken Caton Co., Ltd., and the casing temperature was set to 90.010, and the pressure in the reactor was adjusted to 2.0 MPa and hydrogen. (Valve pressure) From the upper part of the reactor, 10 kg of the composition B obtained above was subjected to M 550 ml / h at 40 ° C. at a rate of r, and hydrogen was allowed to flow through the reactor at a speed of 18.6 Nl / hr. The temperature at the reactor outlet (the bottom of the catalyst layer) was 90.510. The reaction mixture obtained from the reactor outlet was condensed to obtain 10 kg A liquid. The liquid was subjected to the above-mentioned conditions (but the injection temperature was 200 ° C), and a gas chromatograph (manufactured by Shimadzu Scientific Corporation, GC-14B, hydrogen flame ionization detector) was used to analyze the above-mentioned conditions. As a result, the conversion rate of allyl acetate was 99.8%, the selectivity of n-propyl acetate was 99.0¾, the yield of n-propyl acetate was 98.8¾, and the selectivity of acetic acid was 0.9¾. Example 3 A-4 Μ impregnation method carried 45g of palladium and 52g of potassium acetate on 540g of silicon dioxide (surface area 96m2 / g, pore volume 0.78rol / g, average pore radius 115nm, bulk density 540g / l) to obtain a particle diameter of 5mm 1JI catalyst. 60- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ----------- installation -------- order --- ------ Φ (Please read the notes on the back before filling this page)

B7____ 相 I 充 499421 Ⅴ. Description of the invention (1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, so that the 1JI catalyst thus obtained is filled in a stainless steel anti-M device with a diameter of 27ιτ I &gt; 12: Mole% isobutylene, 7.5 Mole% oxygen, 9.0 Mole% acetic acid, 71.5 Mole% dilute gas and heat under the above catalyst at a space velocity of 1 8 0 0 / hr supply &gt; Μ reaction pressure 0.4 MPa (valve) pre-K reaction 〇 cooling the resulting reaction generated gas Μ separation into non-condensing components and condensing components t The reaction crude liquid was distilled to the top of the white tower to obtain the following Composition (hereinafter referred to as plant composition E ") C) <composition E> methacrylic acetate 97.7 wt% allyl alcohol 0.1 wt% acetic acid 2.0 V t% other 0, 2 V t% make 5 0 0 ra 1 activated alumina (manufactured by Putian Pharmaceutical Co., Ltd. &gt; trade name Dunmita 61) A glass reactor with a diameter of 100 ram was filled and the space velocity M was 1 / hr (that is, 500 m 1 / hr). The composition E obtained above was circulated to prepare a mixture of the following composition ( Hereinafter referred to as "composition F j) 〇" composition F &gt; fluorenyl acetate 99.6 wt% allyl alcohol Q · 1 wt% acetic acid 0.1 wt S: other 0.2 wt% 1 Figure ♦ A stainless steel cylindrical reverse trig reactor with a sleeve of 20 mm inner diameter is filled with 130 ml of a supported palladium catalyst (alumina carrier diameter 3 no im X length 3 mm pellets, palladium content 0 . 3% specific surface area 100m 2 / g Yanuyi Kem Caton (strand) y and the jacket temperature is set to 90 • 0 ♦ The pressure in the reactor is adjusted to 1. OMPa (valve pressure) with hydrogen. 〇 Bai Fan 61 61 (Please read the precautions on the reverse side before filling out this page) The paper size applies to China National Standard (CNS) A4 (21 0 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 _B7 _ V. Description of the invention (1 Above the reactor, make 10 kg of the composition F obtained above at 405 ml at 550 ml / hr. And a rate of hydrogen K18.6 Nl / hr was passed through the reactor. The temperature at the reactor outlet (bottom of the catalyst layer) was 90.51C. The reaction mixture obtained from the reactor outlet was condensed to obtain 10 kg of a liquid. The liquid was subjected to the above-mentioned conditions (but the spray temperature was 200 1) and analyzed by gas chromatography K. The conversion rate of methyl allyl acetate was 100.0¾, and the selectivity of isobutyl acetate was 99.0¾. The yield of isobutyl acetate was 99.0¾, and the selectivity of acetic acid was 0.8%. Example 3B-1 Referring to Figure 1, a cylindrical stainless steel reactor with an inner diameter of 20mro Φ and a sleeve was filled with 130ml of a supported palladium catalyst (alumina carrier, diameter 3mm × length 3mm pellets, IB content 0.3 ¾, specific surface area 100m 2 / g, made by Yeniukken Caton (strand), and the sleeve temperature is set to 90.0 ° C, so that the pressure in the reactor is adjusted to 1.0MPa (valve pressure) with hydrogen. From the upper part of the reactor, 10 kg of the above-mentioned composition A (acetic acid content 2.0 WU) was passed at a rate of M550 ml / hr at 40 ° C, and hydrogen at a rate of M18,6 Nl / hr was passed through the reactor. The temperature at the outlet of the reactor (bottom of the catalyst layer) was 9 0, 5 0C. The reaction mixture obtained from the reactor outlet was condensed to obtain 10 kg of a liquid. The liquid was analyzed by gas chromatography to K. The conversion of allyl acetate was 99.92, the selectivity of n-propyl acetate was 97.0¾, and the yield of n-propyl acetate was 96.9¾, and The selectivity of acetic acid is 2. 9¾ 〇 3B-2 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) ---- Order --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 B7 _ V. Description of the invention (61) Refer to Figure 1, a cylindrical reactor made of stainless steel with an inner diameter of 20ηιιηΦ and a sleeve Fill 130ml load-type rhenium catalyst (alumina carrier, diameter 3mmX length 3mro pellets, rhodium content 0.3%, specific surface area 100m2 / g, made by Yeniukum Karton (stock)), and make the casing temperature The pressure M in the reactor was set to 90.0 ° C to 1.0 MPa (valve pressure). From the upper part of the reactor, 10 kg of the above-mentioned composition C (acetic acid content: 2.0 wU) was passed at a rate of 550 inl / hr at 40 ¾, and hydrogen was passed through the reactor at a rate of 18.6 Nl / hr. The temperature at the reactor outlet (bottom of the catalyst layer) was 90 · 5C 0 to condense the reaction mixture obtained from the reactor outlet to obtain 10 kg of a liquid. As a result of analyzing the liquid by gas chromatography with M, the conversion of allyl acetate was 99.92, the selectivity of n-propyl acetate was 97.0%, and the yield of n-propyl acetate was 96.9¾, and The selectivity of acetic acid is 2. 9¾ 〇 Example 3B-3 Referring to the first figure, a cylindrical reactor made of stainless steel with an inner diameter of 20 μm and a sleeve is filled with 130 ml of a supported ruthenium catalyst (alumina carrier, diameter 3 μm). 3mm length pellets, ruthenium content of 0.55¾, specific surface area of 100m2 / g, manufactured by Yeniuk Kemton (share), and the sleeve temperature was set to 90.0 ° C, so that the pressure in the reactor was adjusted to hydrogen. It is l.OMPa (valve pressure). From the upper part of the reactor, 10 kg of the above-mentioned composition A (acetic acid content: 2.0 WU) was passed at a rate of M550 ml / hr at 40 ° C, and hydrogen at a rate of 18,6 Nl / hr was passed through the reactor. The temperature at the reactor outlet (bottom of the catalyst layer) was 90 ° C. One 63 One paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) Packing ----- I--Order ----- -I--. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499421 A7 __B7 _ V. Description of the invention (62) The reaction mixture obtained from the outlet of the reactor is condensed to obtain 10 kg of liquid. As a result of analyzing the liquid by gas chromatography with M, the conversion of allyl acetate was 99.72, the selectivity of n-propyl acetate was 97.0¾, and the yield of n-propyl acetate was 96.7¾, and The selectivity of acetic acid is 2.9%. Example 3B -4 Refer to the first figure, and a cylindrical reactor made of stainless steel with an inner diameter of 20 mm is filled with 130 ml of a supported palladium catalyst (alumina carrier, Diameter 3mfflX length 3mm pellets, rhenium content 0.3¾, specific surface area 100m2 / g, made by Yeniuk Kemton (stock), and the sleeve temperature is set to 90.0 ° C, so that the pressure inside the reactor is hydrogen Adjust to l.OMPa (valve pressure). From the upper part of the reactor, 10 kg of the above-mentioned composition E (acetic acid content: 2.0 wU) was passed at a rate of M550 ml / hr at 40 ° C, and hydrogen was passed through the reactor at a rate of 18.6 Nl / hr. The temperature at the reactor outlet (bottom of the catalyst layer) was 90 ° C. The reaction mixture obtained from the outlet of the reactor was condensed to obtain 10 k g of a liquid. The liquid was analyzed by gas chromatography to M. As a result, the conversion rate of allyl acetate was 99.9%, the selectivity of n-propyl acetate was 97.0¾, and the yield of n-propyl acetate was 96.9¾. And the selectivity of acetic acid is 2. 9¾ 〇 Compare Example 3A-1 and Example 3B-1, and Example 3A-2 and Example 3B-2, Example 3A-3 and Example 3B-3, and Example 3A-4 and Example. 3B-4 shows that the hydrogenated decomposition reaction is suppressed by the present invention, and as a result, a comparable hydrogenated ester can be obtained in a high yield. Industrial use value-64- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) —'--------- ^ ----------- ------ (Please read the notes on the back before filling out this page) 499421 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 _V. Description of the invention (63) As mentioned above, the invention can maintain high Conversion of raw materials, selectivity, and yield enable hydrogenation of unsaturated ester-containing esters to produce hydrogenated esters (especially saturated esters) in industry. No complicated reaction apparatus or reaction engineering is required in the present invention. One aspect of the present invention uses a hydrogenation catalyst that is generally used, and the unsaturated group-containing ester is used as a raw material solution by inertly diluting and diluting the solution in the hydrogenation reaction. Hydrogenated esters. Another aspect of the present invention contains at least one element selected from Group 8 elements, Group 9 elements, and Group 10 of the periodic table at a specific catalyst, that is, the acid point of the K-TPD method is 1. oxicr1 mmol / gM. In the presence of elemental metal hydrogenation catalyst, the hydrogenation reaction of the unsaturated group-containing ester shown in the general formula ⑴ is performed, so that the amount of carboxylic acid generated by hydrogenation is extremely small, and the high conversion and high yield make Saturated esters are converted to hydrogenated esters. In another aspect of the present invention, when an "allylic ester" (general formula η = 1) containing an unsaturated group is used to produce a corresponding hydrogenated ester using a hydrogenation catalyst, the The carboxylic acid concentration in the raw material of the allyl ester is Iv / UM to suppress the hydrogenation decomposition reaction, and a high yield is obtained in a high yield. By this method, hydrogenated esters can be produced industrially and advantageously. (Please read the Zhuyin on the back? Matters before filling out this page) Chang -------- Order ---------. -65- This paper size applies to China National Standard (CNS) A4 specifications 210 X 297 mm)

Claims (1)

499421 6. Patent Application No. 89 1 0681 7 "Method for the Production of Hydrogenated Esters" and its used hydrogenation catalyst and the method for the production of the catalyst "(Amended on March 18, 91) 6. Scope of Patent Application: 1. A method for producing a hydrogenated ester, which is characterized in that an unsaturated group-containing ester represented by the following general formula ⑴ is hydrogenated in the presence of a hydrogenation catalyst to produce a hydrogenated ester shown by the following general formula ，, R 2 R4 R5 (1) (wherein R1, R2, R3, R4, and R5 represent any alkyl group having 1 to 10 carbon atoms, any alkenyl group or hydrogen atom having 1 to 10 carbon atoms, which may be the same If it is not the same, the alkyl or alkenyl group may have a linear or branched chain; R 6 is an arbitrary alkyl group having 1 to 10 carbon atoms, and may have a linear or branched chain; η is 0 or 1) (2) (where η represents 0 or 1; R6 represents 499421 with a carbon number of 1 to 10) 6. Any alkyl group in the scope of patent application; R7, R8, R9, R1Q, and R11 each have independent carbon numbers of 1 to Alkyl group of 10, alkenyl group or hydrogen atom having 1 to 10 carbon atoms) In which the hydrogenation reaction is performed, the concentration of the unsaturated group-containing ester shown in the general formula ⑴ is used for the entire raw material liquid containing the unsaturated group-containing ester. The range is from 1% to 50% by weight. The reaction temperature during the hydrogenation reaction is in the range of 0 ° C to 200 ° C. The hydrogenation catalyst used contains at least one element selected from Group 8 elements, Group 9 elements and Group 10 of the periodic table. Elemental metal, the acid point of the catalyst is 1.0 X 10 ·] mino 1 / g or less. 2. The method for producing a hydrogenated ester according to item 1 of the scope of the patent application, wherein the unsaturated group-containing ester shown in the above general formula ⑴ is diluted with an inert solvent to perform a hydrogenation reaction. 3. The method for preparing hydrogenated esters according to item 2 of the patent application, wherein the inert solvent is a comparable hydrogenated ester. 4. The method for producing hydrogenated esters according to item 3 of the scope of the patent application, wherein the equivalent hydrogenated esters are recovered in part or all of the hydrogenated esters produced by the hydrogenation reaction of the unsaturated group-containing esters shown in the general formula ⑴. 5. The method for preparing a hydrogenated ester according to item 1 of the scope of the patent application, wherein the unsaturated group-containing ester system represented by the general formula ⑴ is one or more selected from the group consisting of allyl acetate, butenyl acetate, methyl allyl acetate, Allyl Propionate, Butyl Propionate, Methyl Allyl Propionate, Vinyl Acetate, Vinyl Propionate, 1, 3-Butadiene Acetate, 1, 3-Butadiene Propionate Groups of compounds. 6. The method for preparing hydrogenated esters according to item 5 of the scope of patent application, wherein the above-mentioned 499421 6. The unsaturated ester containing ester as the raw material is diluted with an inert solvent, and the diluted solution is used as the hydrogenated raw material containing liquid. 7. The method for preparing a hydrogenated ester according to item 6 of the application, wherein the inert solvent is a hydrogenated ester corresponding to the unsaturated ester containing the raw material. 8. The method for producing a hydrogenated ester according to item 1 of the application, wherein the hydrogenation reaction is carried out in a liquid phase reaction using a fixed-layer reaction device. 9. The method for preparing hydrogenated esters according to item 1 of the scope of patent application, wherein in the general formula 对, a hydrogenation catalyst is used for allyl esters of n = l, and a hydrogenation reaction is carried out to produce equivalent hydrogenated esters. The concentration of the carboxylic acid contained in the raw material of the allyl-type ester represented by Formula (I) is 1 wt% or less. 10. The method for preparing a hydrogenated ester according to item 9 of the application, wherein the hydrogenation catalyst contains at least one compound selected from Group 8 elements, Group 9 elements, or Group 10 elements of the periodic table. 1 1. The method for producing a hydrogenated ester according to item 9 of the scope of the patent application, wherein the hydrogenation catalyst is a compound containing at least one compound selected from palladium, germanium, or ruthenium. 1 2 The method for preparing a hydrogenated ester according to item 9 of the scope of the patent application, wherein the allyl ester represented by the general formula ⑴ is at least one selected from the group consisting of allyl acetate, butenyl acetate, methyl allyl acetate, and propyl Allyl esters of allyl acid, butyl propionate, or methyl allyl propionate. 1 3. A hydrogenated ester, which is characterized by being manufactured by a manufacturing method according to any one of claims 1 to 12 in the scope of patent application. 1 4. A hydrogenation catalyst, which is used for the production method of hydrogenated esters according to any one of the scope of patent application No. 499421, patent application scope 1 to 12, and contains at least one element selected from Group 8 of the periodic table, 9 Catalysts for metals of group element and group 10 element, the acid point of the catalyst is 1.0 X 1 0 _ 1 mm ο 1 / g or less. 15. The hydrogenation catalyst according to item 14 of the scope of patent application, wherein at least one metal system selected from Group 8 elements, Group 9 elements and Group 10 elements of the periodic table is at least one selected from palladium, ruthenium, and rhodium . 16. A method for manufacturing a hydrogenation catalyst such as item 14 in the scope of patent application, which is characterized by including at least the following first and second processes; the first process: loading the metal compound at the acid point is 1.0 X 1 0-1 mmol / g or less on a carrier to obtain a carrier carrying a metal compound; the second process: reducing the metal compound of the metal compound carrier obtained in the above first process to obtain hydrogenation Catalyst project. 17. The method for producing a hydrogenation catalyst according to item 16 of the application, wherein the metal compound is a compound containing at least one selected from the group consisting of palladium, ruthenium and rhodium.