TW491835B - Catalyst for production of acetic acid or acetic acid and ethyl acetate, process for its production and process for production of acetic acid or acetic acid and ethyl acetate using it - Google Patents

Abstract

An acetic acid production catalyst that contains (b) at least one element selected from the group consisting of group 14 elements, group 15 elements and group 16 elements of the periodic table and/or (c) at least one element selected from the group consisting of group 6 elements, group 7 elements, group 8 elements, group 9 elements, group 10 elements, group 11 elements and group 12 elements of the periodic table, added to a palladium-loaded catalyst, as well as an acetic acid and ethyl acetate production catalyst that contains (b) at least one compound selected from the group consisting of inorganic acids and salts thereof and/or (c) at least one element selected from the group consisting of group 14 elements, group 15 elements and group 16 elements of the periodic table and/or (d) at least one element selected from the group consisting of group 6 elements, group 7 elements, group 8 elements, group 9 elements, group 10 elements, group 11 elements and group 12 elements of the periodic table, added to palladium.

Description

CO :) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Description of the invention (of the Tongguan application; fa _ _ 8¾ This application is based on one of the applications filed under 35 USC · §lll (b) under 35 USC · § 111 (a), which is based on% usc § 119 (Magic (1) application dated on May 19, 1999, provisional application number 60 / 13-7847, and application date of October 18, 1999, provisional application number 60/1600043 The invention relates to a catalyst for producing acetic acid or acetic acid and ethyl acetate from ethanol and oxygen, a method for producing the catalyst, and a side catalyst for producing acetic acid or acetic acid and ethyl acetate. BACKGROUND OF THE INVENTION Description of the Invention Current industrial processes for the production of acetic acid include a method utilizing the oxidation of acetaldehyde, a method utilizing the reaction of methanol and carbon monoxide, and a method utilizing the oxidation of lower alkanes. Industrially Current methods for the production of ethyl acetate include the acetic reaction of ethanol and acetic acid and the dimerization of ethylene. In recent years, various methods have been studied using ethanol as a starting material to produce acetic acid. As an alternative, an example of a method for producing acetic acid from ethanol in a single stage has been disclosed, which uses copper oxide as the main catalyst, and uses zinc oxide, chromium oxide, and (chromium oxide-manganese oxide) Patent Gazette No. 57_102835). However, because the reaction temperature of this method is as high as 260_36 (rc, and the rideability to acetic acid is insufficient, it is difficult to achieve the actual scale in the industry.

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This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 public love) 491835 A7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economy Palladium is used. For example, acetic acid can be prepared by reacting a metal palladium or a palladium catalyst supported on a carrier such as stone oxide or alumina with ethanol and oxygen (Japanese Examined Patent Publication No. 4S- No. 19292, Brazilian Patent No. 9104562). The palladium catalyst is provided at 100-2. 00. (: the advantage of a relatively low reaction / m degree. However, these methods have a large number of by-products such as acetic acid With the disadvantages of carbon dioxide, it reduces the yield of the target acetic acid. A method using a catalyst packed with metal palladium was disclosed as a method for producing ethyl acetate from ethanol in a single stage. For example, according to

Kunugi and Matsuura% · person (Kogyo Kagaku Zasshi Vol. 71 No. 15 p. 1517 (1968)), using a catalyst of metal palladium loaded on a support of activated carbon, 7_alumina, etc. Acetyl acetate produced with oxygen. It is also possible to use a metal oxide catalyst (Brazilian Patent No. 8901776) to prepare ethyl acetate from ethanol and oxygen. However, these methods have the disadvantages of low ethanol conversion and the generation of a large amount of by-products such as acetic acid, methylamine, and carbon dioxide, which reduces the yield of the target ethyl acetate. A catalyst has also been disclosed, which includes a palladium composition and crystalline titanium pyrophosphate (TiP207) (Japanese Unexamined Patent Publication No. 4_300851). Among them, it has been reported that the production activity of ethyl acetate is enhanced by using a binary catalyst having titanium pyrophosphate as a main component, but even so, the method still has low activity of ethyl acetate production, and The application is not enough for industrial scale. On the other hand, the method using palladium as a catalyst can apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) at a relatively mild paper size -------------- Shang -------- Order --------- Line (Please read the precautions on the back before filling this page) 835

5. Description of the invention (

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Under the reaction conditions, acetic acid and / or ethyl acetate were produced from ethanol and oxygen. Nonetheless', in terms of industrial scale production, a catalyst that is strongly needed is one that can catalyze the reactor with higher activity and higher selectivity. Inventory of Blessings of the Invention One object of the present invention is to provide a catalyst for producing acetic acid or acetic acid and ethyl acetate from ethanol and oxygen, and a method for producing ethyl acetate or acetic acid and ethyl acetate using the catalyst. In order to achieve this goal, the present inventors have devoted research to the expectation that in a method for producing acetic acid or acetic acid and ethyl acetate from ethanol and oxygen by using a catalyst, the performance of the catalyst is further improved, and as a result, a low The invention has been accomplished in terms of catalysts for carbon dioxide selectivity, high activity and long life. In more detail, the present invention is a catalyst for producing acetic acid, which is a catalyst used in a method for producing acetic acid by the reaction of ethanol and oxygen, and includes (a) a metal fixed on a support Palladium and 0) at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table. The present invention (II) is a catalyst for producing acetic acid, which is a catalyst used in a method for producing acetic acid by the reaction of ethanol and oxygen, and includes (a) the metal age fixed on a support And (c) at least one element selected from the group consisting of elements of the sixth, seventh, eighth, nineth, and tenth of the periodic table. The present invention (III) is a catalyst for the production of acetic acid, which is used for the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order · 丨 丨 —— 丨 ——- 6. Description of the invention (4) A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-a kind of acetic acid produced by the reaction of ethanol and oxygen One of the catalysts' and its method comprises palladium metal palladium immobilized on a support, (b) at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table, and at least one selected from rhenium Elements from the following groups: Elements of groups 6, 7, 8, _9, 10, 11 and 12 of the periodic table. The present invention (iv) is a method for producing a catalyst according to any one of inventions ⑴ to invention (ιπ). The present invention (V) is a method for producing acetic acid from ethanol and oxygen, which uses a catalyst according to any one of inventions VII to (III). The present invention (VI) is a catalyst for producing acetic acid and ethyl acetate, which is a catalyst used in a method for producing acetic acid and ethyl acetate by the reaction of ethanol and oxygen, and includes a 0) metal age on the support and (b) at least one compound selected from the group consisting of acid salts and salts thereof. The present invention (VII) is a catalyst for producing acetic acid and ethyl acetate, which is a catalyst used in a method for producing acetic acid and ethyl acetate by the reaction of ethanol and oxygen, and includes (a) Metal palladium, (b) at least one compound selected from the group consisting of: acid salts and salts thereof, and (c) at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table. The present invention (VIII) is a catalyst for producing acetic acid and ethyl acetate, which is a catalyst used in a method for producing acetic acid and ethyl acetate by the reaction of ethanol and oxygen, and includes (a) Metal handle, (b) At least this paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Binding. • Line 491835 A7 V. Description of the invention ( A compound selected from the group consisting of: • no acid salt and its salts, and (at least one element selected from the group: • groups 6, 7, 8, 9, ⑺, 11 and 12 of the periodic table The present invention (IX) is a catalyst for producing acetic acid and ethyl acetate, which is a catalyst used in a method for producing acetic acid and ethyl acetate by the reaction of ethanol and oxygen, and includes 0 ) Metal palladium, (b) at least one compound selected from the following group: · acid-free salts and their salts, (c) at least one element selected from the group: elements of groups 14, 15 and 16 of the periodic table , And (d) at least one element selected from the group: Elements of Groups 6, 7, 8, 9, 10, 11 and 12. The present invention (X) is a catalyst for producing acetic acid and ethyl acetate as in any of the inventions (VI) to (IX), The catalyst is fixed on a carrier. The invention (XI) is a method for manufacturing the catalyst according to any one of the inventions (VI) to (IX), wherein the catalyst is fixed on a carrier. The invention (XII) printed by the Intellectual Property Bureau employee consumer cooperative is a method for manufacturing a catalyst fixed on a carrier as the invention (X). The invention (XIII) is a method for producing acetic acid from ethanol and oxygen and The method of ethyl acetate uses a catalyst such as any one of invention (VI) to invention (χ). I. The best hibiscus of the invention i First, a catalyst for producing acetic acid such as the invention will be described. This paper size applies to Zhongguanjia standard (3k_s) A4 size (21G x 297 public meals 491835 A7

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Printed for the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (The gap volume is preferably about 0.2 to 2 milliliters, more preferably 0.3 to 15 milliliters. The ratio of the carrier The surface area is not particularly limited. The specific surface area per gram of the carrier is preferably from 20 to 800 square meters, and more preferably from 50 to 500 square meters. There is no particular limitation on the pore diameter of the carrier. In the range of 丨 to 2000 μm, more preferably 3 to 8000 nanometers. For example, the invention (I) is a catalyst for producing acetic acid, which is a binary catalytic plutonium which contains (a) metal palladium and An element of group (b). Although the structure of the catalyst is not fully elucidated, palladium is a metal palladium, and group (b) is a metal, a compound, or an alloy with metal palladium, and when When combined, it is believed to exist in a very close manner. Therefore, (&) metal palladium interacts with the group (b) elements to exhibit a very high activity and selectivity. (A) Metal handles one or more The composition ratio of group (b) elements is better (a) l grams: (b) 0.00 5 to 10 g, more preferably (a) 1 g: (b) 001 to 5 g. (A) The amount of metal palladium relative to the carrier will vary depending on the particle size and pore structure of the carrier, but In general, it is preferably in the range of 0.05-10% by weight relative to the support. Even if the loading of palladium is less than 0.01% by weight, the reaction will still proceed appropriately, but it represents a risk of lower productivity. At the same time Even if the loading of palladium is higher than 10% by weight, the reaction will still proceed appropriately, but the high price of palladium makes it undesirable in terms of economics and practical aspects. In fact, the range is preferably 0.2. -6% by weight. Here, "weight%" with respect to the carrier refers to the value obtained by dividing the weight of the metal palladium by the weight of the carrier. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ 297) %) IJ --- Ί .----------- Γ -------- Μ0 (Please read the precautions on the back before filling this page) 10-491835

V. Description of the invention (8) The loading amount of elements in the group VIII with respect to the carrier will vary depending on the particle size and pore structure of the carrier, but it is preferably in the range of 0 to 3 wt% relative to the carrier. , More preferably in the range of __2 ()% by weight. Here, "% by weight relative to the carrier" refers to a value obtained by dividing the weight of the element of the group 以 by the weight of the carrier. For example, the amount of the component of the catalyst of the invention (I) can be measured in the following manner. Use After grinding a predetermined amount of the catalyst into a uniform powder with a mortar, etc., an acid such as hydrofluoric acid or aqua regia is added, and a homogeneous solution is prepared by dissolving it with heating and stirring. Then it is released by plasma. Analyzer device (such as SPS-π〇〇 by Seiko Electronic Industries, KK) to quantitatively analyze the solution. Using standard reagents of different elements that are commercially available, the accuracy of the device can be easily adjusted and repeatable Quantitative effect. A catalyst for producing acetic acid such as invention (II) will now be explained. The catalyst of invention (II) is a catalyst for producing acetic acid, which is used for producing acetic acid by the reaction of ethanol and oxygen. One of the catalysts' and its method comprises (a) metallic palladium and (c) at least one element selected from the group consisting of: a, a periodic table, 10, 丨 丨, and 丨 Group II elements (hereinafter referred to as group (c) elements). (A) The metal palladium in the catalyst of the invention (II) is the same as the catalyst of the invention ⑴. The carrier is also the same as the invention (I ) Catalyst is the same. The catalyst of the invention (II) in the periodic table group 6, 7, 8, 9, 10, 11 and 12 elements, including in detail, complex, gold, gold, recorded, nail, etc. Not installed -------- Order. (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

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 11 835 A7 B7 V. Description of the invention (9) Limited to these elements. From the viewpoint of catalyst performance and practicability, preferable group (C) elements are zinc, gold, and chromium. For example, the catalyst for the production of acetic acid according to the invention (II) is a binary catalyst comprising (a) metal palladium and a group (c) element. Although the structure of the catalyst is not fully elucidated, the palladium is metallic palladium, and the group elements are in the form of a metal, a compound, or an alloy with metallic palladium, and when combined, it is believed to be very Tight way exists. Therefore, compared with the catalysts of conventional techniques, (a) metal palladium interacts with the elements of the ((:) group to display a very high activity and selectivity, and exhibits a very low selectivity to dioxide and excellent selectivity. The activity and selectivity of acetic acid production. The composition ratio of the rhenium metal rhenium to one or more rhenium group elements of the catalyst of the invention (II) is preferably ⑷1 gram: ⑷ to ⑺ gram, more preferably (a) i gram : (C) 0.01 to 5 g. (A) The loading amount of metal palladium relative to the carrier is the same as the catalyst of invention (I). (The loading amount of group 0 elements relative to the carrier will depend on the particle size of the carrier and The pore structure is different, but it is preferably in the range of 0.0001-3% by weight with respect to the carrier, and more preferably in the range of 2g% by weight of the G team. Here, "wt%" with respect to the carrier refers to ( c) The value obtained by dividing the weight of the group element by the weight of the support. For example, the amount of the constituents of the catalyst of each (II) is measured in the same manner as that of the catalyst used in the invention (i). A catalyst used to make acetic acid. (Please read first Note on the back, please fill out this page again) ▼ Install -------- Order --------- line * Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 12 V. Description of Invention (10) The catalyst of () is a catalyst for producing acetic acid, which is a catalyst used in a method for producing acetic acid by the reaction of ethanol and oxygen, and it includes palladium metal, which is fixed on a carrier, (b) at least one it element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table and ⑷ at least one element selected from the group of the periodic table ·, 7, 8, 9, 10 of the periodic table Elements of Groups 11, 11 and 12. The catalyst for plutonium metal in Maoyue (III) catalyst is the same as the catalyst for plutonium. The carrier is also the same as the catalyst for invention (I). The periodic table in the catalyst for invention (III) The elements of groups 14, 15 and 16 are the same as the catalysts of invention VII, and the elements of Groups 7, 8, 9, 10, 11 and 12 of the periodic table in the catalysts of invention _ are the same as the catalysts of invention (π). The carrier is also the same as the catalyst of invention (II). For example, the catalyst used in the invention (III) to produce acetic acid is a three-way catalytic hJ containing (a) metal palladium, a (b) group element, and a ((:) group element. Although the structure of the catalyst is not completely Clarify that when the elements b and (), ,, and the elements of group (C) are each a metal, a compound, or an alloy with metal M, and t are combined, it is believed to be based on It exists in a very tight manner. Therefore, compared with the catalysts of conventional techniques, the palladium metal, (b) group elements interact with the ((:) group element to show a very high activity and selectivity, and show a very high Low CO2 selectivity and excellent acetic acid production activity and selectivity. The composition ratio of (a) metal palladium, one or more (b) group elements and—or more group ⑷ elements in the catalyst of invention (III), preferably ⑷n 297 mm) CNS) A4 specification (21〇; 835 835 V. Description of the invention (11 to 10 g: ⑷0.005 to 10 g, more preferably ⑷1 g ·· ⑻0.01 to 5 g: (c) 0.01 to 5 g (A) The loading amount of metal palladium and (b) group elements relative to the carrier is the same as the catalyst of the invention ⑴, and the loading amount of the group 元素 element is the same as the catalyst of the invention 如. For example, the catalyst of the invention (III) The amount of the constituent components is measured in the same manner as the catalyst used in the invention (I). The method such as the invention (IV) will now be described. The method of the invention (IV) is used to manufacture the invention (1), („ ) And (111) A catalyst for producing acetic acid. A catalyst for producing acetic acid, such as invention ⑴, can be produced by the following production method (1) or (2). A catalyst for producing acetic acid, such as invention (I) The manufacturing method (1) includes the following first and second steps. The first step is a step in which (3) Palladium is loaded on a support to prepare a catalyst filled with metallic palladium. Step 2 is a step in which (b) at least one element selected from the group consisting of Groups 14, 15 and 16 of the Periodic Table Element is packed on a catalyst filled with metal palladium obtained in the first step to obtain a catalyst for producing acetic acid. A production method (2) for a catalyst for producing acetic acid such as the invention (I), Included in this book, the Zhang scale L is in accordance with Chinese national standards (CNs ... Specifications).

(Please read the notes on the back before filling this page) / -------- ^ ^ -------- ^ _ A7 ---------- B7 .____ 、 V. Description of the invention () • Include the following first and second steps. The first step is step 'wherein a palladium compound and (b) at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table are loaded on a carrier to obtain a palladium-filled Catalysts for compounds. The second step is a step in which a catalyst filled with a palladium compound prepared in the first step is reduced to obtain a catalyst for producing acetic acid. In the first step of the method (1) for producing a catalyst for producing acetic acid, such as osmium, the palladium compound is used as a starting material for metallic palladium, and no particular limitation is imposed on it. In most cases, compounds that can be converted to metallic palladium can be used, such as compounds such as vaporized palladium, organic acid salts such as palladium acetate, and also palladium nitrate, palladium oxide, palladium sulfate, and sodium tetrapalladate. As well as the metal itself. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs There is no particular limitation on the method for loading metal palladium or a palladium compound that can be converted into metal palladium on the carrier, and it can be filled by any method. For example, when loading a palladium compound that can be converted into metallic palladium, the compound can be dissolved or suspended in a suitable solvent such as water or propane, an inorganic or organic acid such as hydrogen acid, nitric acid, acetic acid, etc. , Bite the solution, then fill it on the carrier and dry it as a method of filling on the carrier. As the filling method, a dipping method, a method for evaporating to dryness, a kneading method, and a spraying method can also be mentioned, but are not limited to these methods. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 15 Λ835

Description of the invention (13) Although printed by a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, although it is filled with a palladium compound that can be converted into metal palladium, there is no special treatment for the subsequent method for converting the palladium compound to metal palladium, that is, reduction treatment. limits. The reduction treatment may be performed in a liquid phase or a gas phase as long as these conditions are general reduction conditions, and there is no particular limitation. The liquid phase reduction treatment is generally carried out at room temperature, but it can also be carried out by heating to a relatively high temperature, in detail about 30-50t. The gas-phase reduction treatment is preferably carried out by heating the carrier filled with a palladium compound to about 100-60 (rc) to completely convert to a metal. In more detail, a method may be mentioned which is directly or with hydroxide After treatment with an aqueous solution of sodium, barium hydroxide, sodium metasilicate, etc. to convert the palladium compound to an oxide, hydroxide, etc., the palladium compound is reduced to hydrazine, formaldehyde solution, hydrogen, methanol, ethylene, etc. Metal palladium. A method for converting a palladium compound that can be converted into metal palladium to metal palladium can be performed after the catalyst containing the palladium compound is separated, or it can be performed immediately after the filling method. If conditions permit, it is preferably It is performed immediately after the filling method without separation. If necessary, the filling can be stimulated by ordinary methods, and then washed and dried to remove any substances that inhibit the catalytic reaction, such as halides or sodium. Basic salts, etc. can be used to prepare a catalyst filled with metal palladium in the manner described above. Step 2 of the manufacturing method (1) of the catalyst for manufacturing acetic acid as the invention (I) , Is a step in which (b) at least one element selected from the following group · elements of groups 14, 15 and 16 of the periodic table are packed in step 丨 \-; ------ --W —------- ^ 丨 Order -------- line (Please read the precautions on the back before filling in this page)

491835

One is a catalyst loaded with metal palladium for acid production. -In the kind of element used to make B to ⑻at least—㈣ from the bottom of the towel: the starting materials of groups το prime of groups 14, 15 and 16 of the periodic table, there is no special restriction, and it can be vansu itself or The halide, nitrate, acetate, dish, sulfate, or oxide containing the element 'or even a complex having an organic molecule such as acetamidine or nitrile as a ligand. In more detail, gaseous species such as gaseous selenium, pound chloride, antimony chloride, tin gaseous, bismuth gaseous, lead gaseous, etc .; nitrates such as antimony nitrate, tin nitrate, nitrate M, nitrate Etc .; acetates such as tin acetate, bismuth acetate, acetic acid, etc .; and lithiac, lithiac (H2Se〇4) and its salts, selenite (H2Se〇3) and its salts, metal selenium, Oxidized pounds, acetic acid (H6Te〇6) and its salts, pound acid (HJeO3) and its salts, metal pounds, etc., but not limited to these substances. There are no particular restrictions on the method for filling the starting material of group (b) elements on the carrier, and it can be filled by any method. For example, the starting material of group (b) elements can be dissolved or suspended in a suitable one! Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs> Cereals such as water or acetone, an inorganic or organic acid such as hydrogen acid, nitrate | Acid, acetic acid, etc., then dipped into the carrier and dried, as a method of filling on the carrier. !

I As a filling method, the dipping method, the evaporation to dryness method | the kneading method and the spraying method can also be mentioned, but it is not limited to these methods. I 丨 Can be used to produce a catalyst for the production of acetic acid as described in (I) above | Paper size _ (CNS) A4 size coffee x 297 public love) 17 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative 491835 V. DESCRIPTION OF THE INVENTION (I5) Chemical agent. In the first step of the method (2) for producing a catalyst for producing acetic acid as in the invention (1), a palladium compound and (1)) are selected from at least one element selected from the group consisting of: · 14th Periodic Table Elements of Groups 15, 15 and 16 are packed on a carrier to prepare a catalyst filled with a palladium compound. In the first step of the production method (2) of a catalyst for producing acetic acid, such as invented osmium, a palladium compound is used as a starting material for metal palladium, and a method for charging the same, and a method for producing a catalyst for producing acetic acid, such as invented osmium (Ι) The first step is the same. The starting material of the group (b) element and its filling method are also the same as the second step of the manufacturing method (1) for the catalyst for manufacturing acetic acid such as the invention (I). The effect of loading a palladium compound which can be converted into metallic palladium on a support and the effect of loading a starting material of the element of group (b) on a support can be performed in either order. That is, the two filling effects can be performed simultaneously or one after the other. However, the effect of loading the group (b) elements on the carrier is preferably performed simultaneously with the loading of the compound. A catalyst filled with a palladium compound can be obtained in the above manner. In the second step of the method (2) for producing a catalyst for producing acetic acid as in the invention (I), the catalyst filled with a palladium compound obtained in the first step is relocated to obtain an acetic acid for producing acetic acid. The catalyst. For a catalyst having a palladium compound and / or a starting material of group (b) which can be converted to metallic palladium, which is fixed on a support, for a method for converting these compounds into its individual elements, that is, It is used to restore the Chinese standard (CNS) A4 size of this paper (21 × X 297) «Γ

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Jade and invention description (16) There is no special restriction on the method of printing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The reduction treatment is the same as the first step of the production method (丨) of the catalyst for producing acetic acid as in the invention (I). A catalyst for producing acetic acid as in the invention (I) can be obtained in the above-mentioned manner. A catalyst for producing acetic acid as in the invention (II) can be produced by the following production method (3) or (4). The method (3) for producing a catalyst for producing acetic acid as in the invention (II) includes the following first and second steps. The first step is a step in which (0 metal palladium is packed on a support to obtain a catalyst filled with metal palladium. The second step is a step in which (c) at least one selected from the group consisting of Elements: Group 6, 7, 8, 9 '10, 11, and 12 elements of the periodic table are loaded on a metal-palladium-filled catalyst prepared in the first step to prepare a catalyst for producing acetic acid. The method (4) for producing a catalyst for producing acetic acid as the invention (II) includes the following first and second steps. The first step is a step in which a compound and (c) are selected from at least one of the following groups Elements in: Periodic Table 6, 7, 8, 9, 10, 11 and 12 elements are loaded on a carrier to produce a catalyst filled with a palladium compound. 0 This paper size applies to Chinese National Standards (CNS) A4 specifications (21〇x 297 mm) 19-— — — — — — — — — — — — — — — — — — — 1111111 · (Please read the notes on the back before filling this page) 491835

Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economics is a step' in which the catalyst loaded with tritium compounds obtained in the first step is reduced to produce a catalyst for producing acetic acid. -In the first step of the method for producing a catalyst for producing acetic acid according to the invention (11), the palladium compound is used as a starting material of metal palladium, and its filling method and method for converting it to metal palladium are used. The i-th step of the production method (1) of the catalyst for producing acetic acid as invented is the same. In the second step of the method (3) for producing a catalyst for producing acetic acid as in the invention (II), at least one element selected from the group consisting of rhenium is selected from the group consisting of 6, 7, 8, 9, 10 of the periodic table. Elements of Groups 1, 1 and 12 are loaded on a metal-palladium-loaded catalyst prepared in the first step to obtain a catalyst for producing acetic acid. (C) At least one element selected from the group consisting of elements of Groups 6, 7, 8, 9, 10, 11, and 12 of the periodic table is not particularly limited, and it may be 7L element itself or Halides, nitrates, acetates, phosphates, sulfates, or oxides containing the element, or even complexes with an organic molecule such as ethyl acetate or nitrile as a ligand. In more detail, gaseous species such as gasified chromium, gasified manganese, gaseous baht, gaseous ruthenium, gaseous rhodium, gaseous iridium, nickel chloride, tetrakisaurate and its salts, gaseous Compounds such as zinc gas, etc .; nitrates such as chromium nitrate, nitrate, nickel nitrate, iridium nitrate, zinc nitrate, etc .; acetates such as chromium acetate, manganese acetate, baht acetate, ruthenium acetate, iridium acetate, nickel acetate, zinc acetate, etc. ; But not limited to these substances. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

Ί.—ι · ^ ρ Binding h -------- Line Win (Please read the notes on the back before filling this page) 20 A7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (18) There is no special restriction on the method for filling the starting material of group (c) elements on the carrier, and any method can be used. Method. For example, the starting material of group (b) can be dissolved or suspended in a suitable solvent such as water or acetone, an inorganic acid or organic acid such as hydrogen acid, nitric acid, acetic acid, etc., and then impregnated into the carrier and It is dried as a method for loading on a carrier. As the method of filling, mention may be made of the dipping method, the method of blowing to dryness, the kneading method, and the spraying method, but it is not limited to these methods. A catalyst for producing acetic acid as invented can be obtained in the above-mentioned manner. In the method (4) for producing a catalyst for producing acetic acid as in the invention (II), in the first step, a palladium compound and (C) at least one element selected from the group consisting of: Periodic Table 6, 7, 8 Elements of Groups 9, 9, 10, 11 and 12 are packed on a carrier to prepare a catalyst filled with a palladium compound. In the manufacturing method of the catalyst for manufacturing acetic acid such as the invention (II) (4) The chemical & system is used as the starting material of the metal, its filling method, and the manufacturing method of the catalyst for manufacturing acetic acid with the invention (i.e. 1) Step 1; Same. The starting material of the group (c) element and its filling method are also the same as the second step of the production method of a catalyst for producing acetic acid such as ⑴. The effect of loading a palladium compound that can be converted into metallic palladium on a carrier j The effect of loading a starting material of the group (c) elements on a carrier can be performed in any order. That is, the two filling effects can be performed at the same time, or the previous one < this paper size is applicable to Zhongguan specifications coffee 挪 Nuo Gongai) --------------- packing ---- ---- Order --------- Line (Please read the phonetic on the back? Matters before filling out this page} -21 491835

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (19). However, the effect of loading the group (c) element on the carrier is preferably performed simultaneously with the loading of the palladium compound. A catalyst filled with a palladium compound can be obtained in the above manner. In the second step of the method for producing a catalyst for producing acetic acid, such as the invention (Π), the catalyst containing the amidine compound prepared in the first step is reduced to obtain a catalyst for producing acetic acid. In the case of a catalyst having a palladium compound and / or a group (c) element starting material which is immobilized on a support and which is converted to metallic palladium, for a method for converting these compounds into their individual elements, that is, There is no particular limitation on the method for the reduction treatment by tritium. The reduction treatment is the same as the first step of the method for producing a catalyst for producing acetic acid such as ⑴. A catalyst for producing acetic acid as invented (π) can be obtained in the above-mentioned manner. A catalyst for producing acetic acid such as the invention (III) can be produced by the following production methods (5) to (8). A method (5) for producing a catalyst for producing acetic acid, such as the invention (HI), includes the following first and second steps. The first step is a step in which metal palladium is loaded on a support to obtain a catalyst filled with metal palladium. The second step is a step in which (b) at least one element selected from the group 14, 15 and 16 of the Periodic Group of the Elements and (c) at least one element selected from the following are selected from the following Chinese paper standards (CNS) ) A4 specification (210 X 297 issued) J ----------- ^ 丨 Order --------- line (Please read the precautions on the back before filling this page) 22 A7 A7 〇 Consumption Cooperation of Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs-V. Invention Description (20): Elements in the Periodic Table of Elements 6, 7, 8, 9, 10, "and elements of ⑵ 矣, produced by Step 1 A catalyst obtained by filling the catalyst of the metal age to obtain a catalyst for producing acetic acid. A method (6) for manufacturing a catalyst for producing acetic acid by using X such as invention (II), including the following first and second steps Step 1 is a step in which at least one compound is selected from the group consisting of elements of Groups 14, 15 and 16 of the H Periodic Table and at least one element selected from the group: The 7, 8, 9, 10, 11 and 12 known π reads and fills on the _ carrier to obtain _ kinds of catalysts filled with compounds. Step 2 In the second step, a catalyst filled with a palladium compound obtained in the first step is reduced to obtain a catalyst for producing acetic acid. A method for producing a catalyst for producing acetic acid such as the invention (m) (ie, includes The following steps 1 to 3. Step 1 is a step 'wherein a palladium compound and rhenium are selected from at least one element selected from the group consisting of: 14, 15, and 16 rhenium elements on a carrier to obtain A catalyst filled with a palladium compound. The second step is a step in which a catalyst compound filled with a periodonium compound prepared in the first step is reduced to obtain a catalyst having a gold limb.

------------- install -------- order --------- line (please read the precautions on the back before filling this page) 23 f 1835

V. Description of the invention (21) Step 3 (please read the notes on the back before filling out this page) is a step in which (c) at least one element selected from the following groups: • Periodic Table 6, 7, Elements of groups 8, 9, 10, 11 and 12 are packed on a metal-filled catalyst prepared in the second step to obtain a catalyst for producing acetic acid. The production method (8) of the catalyst for producing acetic acid as the invention (III) includes the following first to third steps. Step 1 is a step in which a palladium compound and (c) at least one element selected from the group consisting of elements of Groups 6, 7, 8, 9, 10, 11 and 12 of the periodic table are packed in a carrier In order to obtain a catalyst filled with a palladium compound. The second step is a step in which a palladium-filled catalyst obtained in the first step is reduced to obtain a metal-palladium-filled catalyst. Step 3 The Department of Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperative Printing Department is a step in which (b) at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table is filled in A catalyst loaded with metal palladium was prepared to obtain a catalyst for producing acetic acid. In the first step of the method (5) for producing a catalyst for producing acetic acid, such as the invention (III), the palladium compound is used as a starting material for metal palladium, and a method for filling the same and a method for converting it into a metal handle are used. According to the invention (I) this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 24 491835 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7. V. Description of the invention (22); The first step of the catalyst manufacturing method (1) is the same. In the second step of the production method (5)-of a catalyst for producing acetic acid as the invention (III), (b) at least one element selected from the group consisting of elements of groups 14, 15, and 16 of the periodic table The first 4 steps and the method of filling are together with the second step of the production method (1) using the catalyst for producing acetic acid as in the invention (I). The starting material of the group (c) element and its filling method are the same as the second step of the manufacturing method (3) of the catalyst for manufacturing acetic acid such as the invention (II). A catalyst for producing acetic acid as in the invention (III) can be obtained in the above-mentioned manner. In the first step of the method (6) for producing a catalyst for producing acetic acid as the invention (III), the palladium compound is used as a starting material for metal palladium, and a method for filling the same and a method for converting it into a metal handle are used. The first step of the production method (1) of the catalyst for producing acetic acid as invented by the invention is the same. The starting material of the elements of group (b) and the method of filling thereof are the same as the second step of the production method (1) for the catalyst for producing acetic acid, such as that of plutonium. The starting materials of the elements of the rhenium group and their filling methods are the same as the second step of the production method (3) of the catalyst for producing acetic acid such as the invention (II). The role of loading the metal compounds that can be converted into metallurgy on the carrier The role of loading the starting material of group (b) elements on the carrier ... The role of loading the starting material of group (c) elements on the carrier, Can be done in any order. That is, all loading effects can be performed at the same time, or _forward_backward advance = ° However, the effect of loading the elements of the group ⑷ on the carrier is preferably the same as the standard paper size of the central paper (CNS) A4 Regarding coffee love for the public --------------- install -------- order --------- line (please read the precautions on the back first) (Fill in this page) A7 V. Description of Invention (23) The loading of objects is performed simultaneously. A catalyst in which rhenium is filled with a palladium compound can be prepared in the manner described above. In the second step of the method (6) for producing a catalyst for producing acetic acid as the invention (III), the catalyst filled with a palladium compound obtained in the first step is reduced to obtain a catalyst for producing acetic acid. catalyst. In the case of a catalyst having a palladium compound fixed on a support, which can be converted into metallic palladium, a starting compound of group (b) elements and / or a starting compound of group (c) elements, The method of conversion into its individual elements, that is, the method for reduction treatment, is not particularly limited. The reduction treatment is the same as the first step of the production method of a catalyst for producing acetic acid such as ⑴. In the first step of the production method (7) of a catalyst for producing acetic acid such as the invention (m), the compound is used as a starting material of a metal handle, and a filling method thereof and a method for converting it into a metal handle are used for For example, the first step of the method for producing a catalyst for producing an acetic acid is the same as that of the invention. A) The starting material of the group element and its filling method are the same as the second step of the manufacturing method of a catalyst for producing acetic acid such as that of the invention. Sequentially. That is, 'the two filling effects may be performed simultaneously, or-one after the other.' However, the effect of loading the elements of the group VIII on the carrier is preferably performed simultaneously with the loading of the compound. Μ The effect of filling compounds on a carrier that can be converted into a metal handle and the effect of filling the starting material of group 03) elements on a carrier can be obtained in any of the above-mentioned manners. catalyst. This paper size applies to Chinese National Standard (CNS) A4 specifications ⑽χ⑽ 公 爱 γ -26-A7-V. Description of the invention (24 (Please read the precautions on the back before filling this page) It is used for manufacturing such as invention (ΠΙ) In the second step of the method (7) for the production of an acetic acid catalyst, the palladium compound filled with the palladium compound prepared in the first step is catalytically reduced to obtain a catalyst filled with metal palladium. As a catalyst for the above-mentioned palladium compound that can be converted into metallic palladium and the starting compound of group 7L element (b), for the method for converting these compounds into their individual elements, that is, the method for reduction treatment There is no particular limitation. The reduction treatment is the same as the first step of the production method (1) of the catalyst for producing acetic acid as invented (I). A metal-filled catalyst can be obtained in the above manner. In use In the third step of the production method (7) of the catalyst for producing acetic acid as the invention (III), the group (c) element is packed on the metal-palladium-filled catalyst obtained in the second step to obtain One used to make B A catalyst for the production of acetic acid, such as the invention (〖Η), can be prepared in the above manner. The manufacturing method for the catalyst for the production of acetic acid, such as the invention (III), is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (8) In step 1), the palladium compound is used as a starting material for metal palladium, and its filling method and method for converting it to metal palladium are related to the method (3) for producing a catalyst for producing acetic acid as invented (H) The first step is the same. (C) The starting material of the group element and its filling method are the same as the second step of the production method (3) for the catalyst for producing acetic acid as invented (II). The metal can be converted into palladium. The effect of filling palladium compounds on the carrier and the loading of the starting material of group (c) elements on the carrier can be in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 public love) according to this paper size. 27 A7 Fifth, the invention description (25), the sequence of advancement, that is, the two filling effects can be performed simultaneously, or one after the other (please read the precautions on the back before filling this page) also order ..., and, will Set of elements The effect on the support is preferably carried out simultaneously with the filling effect of the compound. A catalyst filled with a palladium compound can be prepared in the manner described above.-A method for producing a catalyst for producing acetic acid such as the invention (II) In step 2), the catalyst filled with the princess compound prepared in step 1 is reduced to obtain a kind of «catalyst with gold limbs. For example, there is a catalyst that can be converted to metal palladium fixed on a carrier. As a catalyst for the palladium compound and (c), and the starting compound of the element, for the method used to convert A and other substances into their individual elements, that is, the method used for reduction treatment and thermally special The reduction treatment is the same as the first step of the production method of a catalyst for producing acetic acid as invented. A catalyst filled with metal palladium can be obtained in the above manner. In the third step of the method (8) for producing a catalyst for producing acetic acid as in the invention (III), the group (b) elements are packed on the metal-palladium-filled catalyst obtained in the second step to A catalyst was prepared for the production of acetic acid. The starting material of Group (b) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and its filling method are the same as the second step of the manufacturing method (1) of the catalyst for manufacturing acetic acid such as the invention (I). In the above manner, a catalyst for producing acetic acid as in the invention (111) can be obtained. Invention (V) is a method for producing acetic acid from ethanol and oxygen, which uses any one of inventions (I), (II) or (III) to produce acetic acid. ) A4 specification (210 X 297 mm) 28 A7, description of invention (26) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Catalyst Economy before the reaction method allows the catalyst of the present invention to react with ethanol and oxygen. For this method There is no particular problem, and it can be any of a variety of methods, including a batch method for a gas phase reaction or a liquid phase reaction, a continuous flow method, or a combination thereof. Ethanol starting materials can be supplied in the gas phase or in the liquid phase. That is, the reaction method may be, for example, a semi-continuous method in which the catalyst of the present invention is suspended in liquid ethanol and / or an ethanol solution and oxygen is passed in; or the reaction method may be a continuous flow method in which ethanol and oxygen System passed through the catalyst. The gas phase reaction method is preferred from the standpoint of catalyst, starting material and product separation, and from the viewpoint of acetic acid productivity. The one which is better and more advantageous in terms of practicality is a fixed bed used in a gas-phase reaction method, which has a corrosion-resistant reaction tube 'filled with the catalyst of the present invention, and ethanol and oxygen pass through it. The gas-phase reaction and liquid-phase reaction in the method for producing acetic acid as the invention (V) will now be explained. First, a gas phase reaction will be explained. For example, in the acetic acid production method of the invention (V), there is no particular limitation on the reaction temperature for producing acetic acid by the reaction of ethanol and oxygen in the gas phase, but it is preferably 100-25 (TC. If the reaction temperature Below loot :, the reaction rate is insufficient. If the reaction temperature is higher than 250 ° C, a large number of secondary reactions will tend to occur. As far as applications are concerned, the better line is between ^ 0-23 (^ (: Range. -------------- ^ i — (Please read the precautions on the back before filling this page) _; The size of the thread paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 29

V. Description of the invention (27) As far as the equipment is concerned, there is no particular limitation on the reaction pressure, but in practice it is advantageous from 0.0 to 3.0 MPa (measuring pressure). More preferably, it is in the range of 0 to 1.5 MPa (gauge pressure). In the case of a flow type reaction, the gas supplied to the reaction system < The gas includes ethanol and oxygen, and nitrogen, carbon dioxide, a rare gas, etc. may be used as a diluent if necessary. The amount of ethanol supplied to the reaction system corresponds to a ratio of 0.01 to 50% by volume of the total gas supplied, especially 0 to 40% by volume. /. The amount of oxygen corresponds to a ratio of 1-15 vol%, especially 2-10 vol%. Here, if the ethanol concentration exceeds 20% by volume, the degree of the secondary reaction will increase. On the other hand, if the ethanol concentration is less than 2% by volume, the productivity will tend to decrease. If water is present in the reaction system, it will provide a significant effect of increasing the activity and selectivity of acetic acid production, as well as prolonging the activity of the catalyst in the reaction system. It is suitable to include 0.1-50 volume ❾ / 0 of water vapor in the reaction gas. If the water vapor in the reaction gas is present in an amount of less than 0.01% by volume, the catalyst may be deteriorated more quickly. If the water vapor is present in an amount of more than 50% by volume, the demand for the steam device may be poor. In terms of application, this range is preferably 0.5 to 40% by volume. When the acetic acid production method of the present invention is performed in accordance with the gas phase reaction, there is no particular limitation on the ethanol starting material. It is advantageous to use a high-purity ethanol starting material, but it is not a problem if it is mixed with a small amount of a lower saturated hydrocarbon such as methane, ethane or propane. There is no special restriction on oxygen. It can be in the form of air, and it is a paper standard that punctures the national standard (CNS) A4 specification (21G X 297 public love) ----.--- Ί ^ ---- · --------- ^ — Order · --------- Line (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 30 Invention Description (28) Dilute with an inert gas such as nitrogen or carbon dioxide. When circulating the reaction gas, it is generally advantageous to use high-degree oxygen, preferably 99% or more. It can also be mixed with acetaldehyde or diethyl. It can be mixed with the reaction mixture gas, preferably between the total reaction mixture, and more preferably between 0.01-4.0, the reaction mixture gas-based ether containing ethanol and oxygen, and the acetaldehyde and the acetaldehyde supplied from the reaction system. The amount of diethyl ether is in the range of 0.001-5.0% by volume of the gas, and in the range of% by volume. The volume velocity of the reaction mixture gas passing through the catalyst is preferably in the range of 50 (M5,000 hours ·, especially in the range of 1,000-10,000 hours "in the standard state. The liquid phase will be explained next. Reaction. As in the acetic acid production method of the invention (V), there is no particular limitation on the reaction temperature for producing acetic acid by the reaction of ethanol and oxygen in the liquid phase, but it is preferably 0-200 ° C. If the reaction temperature is lower than 0 ° C, the reaction rate will be insufficient. If the reaction temperature is higher than 200 ° C, a large number of secondary reactions may occur. As far as applications are concerned, it is more preferably between 2 (M0 (TC Range. As far as the equipment is concerned, there is no particular limitation on the reaction pressure, but it is actually advantageous from 0 · 0 to 3.0 MPa (gauge pressure). It is more preferably between 0.001 to 1.5 MPa (gauge pressure). Scope. Ethanol and / or oxygen starting materials can exist in the catalyst beforehand, and can be added at the appropriate point in the reaction. It can be supplied to the reaction system in the form of gas phase or liquid phase. 491835 V. Description of the invention (29 Ministry of Economic Affairs) Printed by Intellectual Property Bureau employee consumer cooperatives to The starting materials of the reaction system include ethanol and oxygen, and nitrogen, carbon dioxide, or a diluent gas can be used if necessary. If water is present in the reaction system, it will provide significant effects to enhance the activity and production of acetic acid, and There is no particular restriction on the ratio of water to ethanol in the reaction system and system to extend the activity of the catalyst in the reaction system and system. During the reaction, even the ratio of water to ethanol can be changed, or a suitable amount of water can be added to Maintain-a constant ratio. If necessary, an experimental component such as sodium hydroxide can be added to increase the reaction rate. When the acetic acid production method of the present invention is performed in accordance with the liquid phase reaction, there is no particularity for the ethanol starting material. The use of high-purity ethanol starting materials is advantageous, but it does not pose a problem if it is mixed with a small amount of lower saturated hydrocarbons such as methane, ethane or propane. There is no particular limitation on oxygen, It can be in the form of air or diluted with an inert gas such as nitrogen or carbon dioxide. When the reaction gas is circulated, a high The degree of oxygen is generally more favorable, preferably more than 99%. The reaction mixture gas or liquid containing ethanol and oxygen can also be mixed with acetaldehyde or diethyl ether and supplied to the reaction system. In the gas phase The acetic acid obtained in the case of reaction or liquid phase reaction can be separated and purified to the desired purity using ordinary methods. When unreacted starting materials and acetaldehyde and / or diethyl ether are retained, For the product, unreacted starting materials and by-products such as acetaldehyde and / or diethyl ether can be recovered into the reaction system for use. (Please read the precautions on the back before filling this page) -.1- ------ Order ---------- Line 1 32 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491835 螓 * A7 _-_ B7 V. Description of Invention (3〇) Catalysts for the production of acetic acid and ethyl acetate, such as inventions (VI) and (X). Invention (VI) is a non-supported fixed catalyst for producing acetic acid and ethyl acetate, which is a catalyst used in a method for producing acetic acid and ethyl acetate by the reaction of ethanol and oxygen, and includes Metal palladium and (b) at least one compound selected from the group consisting of: inorganic acids and their salts (hereinafter referred to as group (b) compounds) or one of the catalysts of the invention (X), which is a A carrier-fixed catalyst for producing acetic acid and ethyl acetate, wherein the specific catalyst composition is fixed on a carrier. The palladium contained in the catalyst of the invention (VI) is metallic palladium, and its valence is zero. Metal palladium can be prepared by delocalizing divalent and / or tetravalent palladium ions using a reducing agent such as hydrazine, hydrogen, or the like. Not all palladium must be in a metal state. As the inorganic acid as the compound of the group (b), phosphoric acid, sulfuric acid, hydrogen acid, nitric acid, niobic acid, heteropolyacid, and the like can be mentioned, but it is not limited thereto. Among them, phosphoric acid or heteropolyacid is preferred. Heteropolyacid is an acid formed by the condensation of two or more inorganic oxyacids containing a coordination element (polyatoms) and a central element η (heteroatoms). For heteroatoms in heteropolyacids, mention may be made of plates, stone slabs, sheds, lu, germanium, osmium, cobalt, chromium, and for polyatoms, molybdenum, tungsten, vanadium, niobium, and Tantalum. Specific examples that can be mentioned are tungstic acid, silicomolybdic acid, molybdic acid, dishic acid, hair tungstic acid, hair tantaly molybdic acid, shed acid, boromolybdic acid, and boromolybdic acid. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------- Installation -------- Order -------- -Line (Please read the precautions on the back before filling this page) 33 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491835 Α7 ____ Β7 V. Description of the Invention (31) The best of these heteropoly acids are miscellaneous The atom is phosphorus or silicon, and the polyatomic system is at least one element selected from the group consisting of tungsten, molybdenum, and vanadium. As the inorganic acid salt of the compound of group (b), mention may be made of metal salts or radium salts in which all or part of the hydrogen atoms of the inorganic acid are substituted. There is no particular restriction on the metal element replacing the hydrogen atom of the inorganic acid. Specific examples are at least one element selected from the group consisting of elements of groups 1, 2, 6, 7, 8, 9, 10, U, 12 and 13 of the periodic table, and examples of the sulfonium salts of inorganic acids include Ammonium or ammonium salts of amines. Particularly preferred among these inorganic acid salts are metal salts of lithium, sodium, potassium, planer, osmium, chromium, barium, cobalt, nickel, manganese and copper. Although the structure of the catalyst is not completely elucidated, palladium is (^ metal palladium, and group (b) is a compound with a clear acidity. According to # (a) and (b) Group II elements and compounds It exists in a very close manner, and the interaction between the elements of each group and the compound shows a very high activity and selectivity. (A) The composition ratio of the metal Ιε to the (b) group of compounds is preferably (a) i g · (b ) 0.025 to 500 grams, more preferably (a) i grams: (b) 〇 丨 to 400 grams. There is no particular limitation on the rhenium metal rhenium content in the catalyst. However, it is preferably between 0.001 and 0.001. -10% by weight range. Even if the content of (a) metal palladium is less than 0.001% by weight, the reaction will still proceed appropriately, but it represents a risk of lower productivity. At the same time, even if (a) metal = content is higher than At 10% by weight, the response will still be appropriately adjusted to make it undesired in terms of economics and practical aspects. Actually ^ '丁' 上 'The paper size of this template applies the Chinese National Standard (CNS) A4 Specifications (210 X 297 mm)-; ---- I ^ ----------- Γ -------- (Please read first Please fill in this page again if you need to pay attention to the above) 34 491835 A7 V. Description of the invention (32 is preferably 0.005-8. 0% by weight. Here, "the weight ratio of the weight of the golden limb of the total weight. Refers to the relative catalysis only with the catalyst material having the above composition, the catalyst, or the catalyst can be packed in-the carrier 2 is used for this purpose. The carrier used for more-favorable alignment is a oxidized stone with suitable porosity, oxidation Ming, oxidized stone-oxidized sand, oxidized earth, montmorillonite and titanium oxide, ion-exchange tree vinegar, polymer-based carriers, etc., of which oxygen cutting is the best. The form of the carrier can be powder, Spheres, pellets, or any other form desired./ The particle size of the carrier is preferably from millimeters to millimeters. When the reaction is carried out by charging the catalyst into a cylindrical reactor, it is less than 1 A particle size of millimeters will generate a large pressure drop when the gas flows through, which may cause an ineffective gas circulation effect. If the particle size is greater than 10 mm, the reaction gas cannot diffuse into the catalyst, which may hinder Effective catalytic reaction. The particle size is more preferably 3-8 mm. B The pore volume of the carrier is preferably about 0.2 to 20 milliliters per gram of carrier, more preferably 0.3 to 1.5 milliliters. The specific surface area is preferably 20-800 square meters per gram of carrier, more preferably 50-500 square meters. The pore diameter of the carrier is preferably ^ 2000 nm, more preferably 3-800 nm. Consumption The amount of the (a) metal handle relative to the carrier printed by the cooperative will vary depending on the particle size and pore structure of the carrier, but generally it is preferably in the range of 0.01 to 10% by weight relative to the carrier. Even if The loading of palladium is less than 0.01% by weight '' The reaction will still proceed appropriately, but it represents a risk of lower productivity. The paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm A7 1 '^ · ~ · .—2Z ____ ___ V. Description of the Invention (33). At the same time, even if the loading of palladium is higher than 10% by weight, the reaction will still proceed appropriately, but the high price of palladium makes it economically and practically unpleasant (please read the precautions on the back before filling this page) Desire. In practice, this range is preferably 0.2 to 6% by weight. Here, "weight%" means the ratio of the amount of (a) metal palladium in the catalyst relative to the weight of the support. The loading amount of the group (b) compound with respect to the carrier will vary depending on the particle size and pore structure of the carrier, but it is preferably in the range of 200% by weight relative to the carrier, and more preferably in the range of 10-100% by weight. Range. Here, "% by weight" refers to the weight ratio of group 0) of the catalyst relative to the weight of the carrier. The invention (VII) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is used to produce acetic acid and ethyl acetate A non-supported fixed catalyst 'is a catalyst used in a method for producing acetic acid and ethyl acetate by the reaction of ethanol and oxygen, and includes (a) a metal age, (b) at least one selected from Compounds in the following groups: inorganic acids and their salts and (c) at least one element selected from the group: elements of groups 14, 15 and 16 of the periodic table (hereinafter referred to as group (c) elements), Or as one of the catalysts of the invention (X), it is a carrier-fixed catalyst for producing acetic acid and ethyl acetate, wherein the components of these catalysts are fixed on a carrier. The catalyst of the invention (VII) It is the catalyst of invention (VI), which contains _ group (c) elements and is a three-way catalyst. (A) The metal handle and (b) compound used in invention (VII) are related to invention (VI) Same. 36 This paper is applicable National Standard (CNS) A4 Specification (210 X 297 mm) 491835 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-V. Description of the Invention (34 (c) Elements of Groups 14, 15 and 16 of the Periodic Table include Selenium , Pound, antimony, tin, bismuth, and lead. Among them, selenium, zinc, tin, and bismuth are preferred. Although the structure of the catalyst has not been fully elucidated, (the young metal palladium and group (b) compounds are used in the invention The catalyst of (VI) is the same, and the same effect as that of the catalyst of invention (vi) can be expected. It is believed that the elements and compounds of the (Heart, (b) & (c) group 3 exist in a very close manner, (Phosphorus palladium, group (b) compounds and group (c) elements therefore show very high activity and selectivity due to their interactions, that is, they exhibit very low selectivity for carbon dioxide and acetaldehyde, while exhibiting excellent acetic acid and acetic acid Ethyl ester production activity and selectivity. The composition ratio of (a) metal palladium, (b) group compounds and group elements in the catalyst is preferably (a) 1 g: (b) 0.025-5500 g: (c) 0.0005 g is more preferably (a) 1 g: (b) 0.1-400 g: 0.005 g. The content of osmium metal palladium in the chemical agent is the same as that of the catalyst of the invention (VI). (The loading amount of group 0 elements with respect to the carrier will vary depending on the particle size and pore structure of the carrier, but it is relative to the carrier. It is preferably in the range of 0.0001-3.G% by weight, and more preferably in the range of 2% by weight. Here, "% by weight" refers to the weight of the element VIII in the catalyst relative to the weight of the support. Invention (VIII) is a non-supported fixed catalyst for producing acetic acid and ethyl acetate, which is a catalyst used in a method for producing acetic acid and ethyl acetate by the reaction of ethanol and oxygen, and It includes rhenium metal palladium, at least-compounds selected from the group: inorganic acids and their salts, and at least-elements selected from the group: Periodic Table 6, 7, 8 ^ ---- ---- ^ --------- ^ (Please read the notes on the back before filling out this page) 37 491835 A7

5. Description of the invention (35), elements of groups 9, 10, 11 and 12 (hereinafter referred to as group (d) elements), or one of the catalysts of the invention (X), which is a kind of acetic acid And B (Please read the notes on the back before filling this page) Supported catalysts for ethyl acetate, in which the catalyst components are fixed on a support. The catalyst of the invention (VIII) is the catalyst of the invention (VI), which comprises a group (d) element and is a three-way catalyst. The rhenium metal palladium and the rhenium group compounds used in the invention (VIII) are the same as those in the invention (VI). With regard to (d) elements of Groups 6, 7, 8, 9, 10, 11 and 12 of the periodic table, Lu 'may mention chromium, manganese, baht, ruthenium, osmium, silver, silver, gold, and zinc. Among them, chromium, manganese, gold and zinc are preferred. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, although the structure of the catalyst is not fully elucidated, (the metal palladium and the (b) compound are the same as those used for the catalyst of the invention (VI), and are expected to be the same as the invention ( VI) catalysts have the same effect. It is believed that the elements and compounds of the (&), (1 ^ and () sentence groups exist in a very close manner. (About metal palladium, group (b) compounds and (d) As a result of the interaction of the group elements, they show a very high activity and selectivity, that is, they exhibit very low selectivity for carbon dioxide and acetaldehyde, and at the same time exhibit excellent activity and selectivity for the production of acetic acid and ethyl acetate. The composition ratio of the metal palladium, the (b) group compound and the (d) group element is preferably (a) l g ... (b) 0.025-500 g ... (d) 0.005-10 g, more preferably (a) 1 g: (b) 0.1-400 g: (d) 0.01-5 g. The content of (a) metal palladium in the catalyst is the same as the catalyst of the invention (VI). The effect of being loaded on a carrier In terms of this carrier, it is also used to invent 38 paper sizes that are in compliance with Chinese National Standard (CNS) A4 regulations. (210 X 297 mm) 491835 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-V. The catalysts of the invention description (36 (VI) are the same. (A) Metal palladium and (b) Group compounds relative to the carrier The loading amount is the same as the catalyst used in the invention (VI). The loading amount of group (d) elements relative to the carrier will vary depending on the particle size and pore structure of the carrier, but it is relative to the carrier. It is preferably in the range of 0.0001 to 3.0% by weight, and more preferably in the range of 0.001 to 2% by weight. Herein, "% by weight" refers to the weight of the group ((1) group of elements in the catalyst relative to the weight of the support). The invention (IX) is an unsupported solid catalyst for the production of acetic acid and ethyl acetate, which is a catalyst used in a method for producing acetic acid and ethyl acetate by the reaction of ethanol and oxygen. And includes (a) metallic palladium, (b) at least one compound selected from the group consisting of: inorganic acids and their salts, (c) at least one element selected from the group consisting of: 14, 15 and 16 of the periodic table Elements of the group and (d) at least one selected from Elements in the columns: elements of Groups 6, 7, 8, 9, 10, 11, and 12 of the periodic table, or one of the catalysts of invention (x), which is used to make acetic acid and ethyl acetate An ester-supported fixed catalyst, in which the catalyst components are fixed on a support. The catalyst of the invention (IX) is the catalyst of the invention (VII), which comprises a group (d) element and is a quaternary catalyst. (A) metal palladium, (b) compounds and (c) elements used in the invention (IX) are the same as those used in the catalyst of the invention (VII). (D) at least one element selected from the group : The paper sizes of Groups 6, 7, 8, 9, 10, ^ and ^ of the Periodic Table are applicable to China National Standard (CNS) A4 (210 X 297 mm) --------- I-- --Installation --------- Order ------- II line (please read the precautions on the back before filling this page) 491835 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs ---- ----- B7______ V. Description of Invention (37) The elements are the same as those of Invention (VIII). Although the structure of the catalyst is not completely elucidated, (the metal palladium, the compounds of group (b) and group (c) are the same as those used in the catalyst of invention (VII), and it is expected that the catalyst of invention (VII) The same effect of the dagger. It is believed that the elements and compounds of the Q), (b), (c) and (d) groups exist in a very close manner. (A) Metal palladium, (b) Group compounds, (Group 0 elements, and (Sentence group elements therefore show very high activity and selectivity due to their interaction, that is, they exhibit very low selectivity for carbon dioxide and acetaldehyde, and at the same time exhibit extreme Excellent production activity and selectivity of acetic acid and ethyl acetate. The ratio of (a) metal age, (b) group compounds, (c) group elements, and (sentence group Fansu) in catalytic A 彳 is better (a) 1 gram: (b) 205.500 grams: (c) 0.005-10 grams: ⑷0.005 to 10 grams, more preferably (^ (b) ○ "Choke: ( c) 0.01-5 g: (d) 0.01-5 g. The content of (a) metal palladium in the catalyst is the same as the catalyst of the invention (VI). The effect of loading on a carrier is In other words, the carrier is also the same as the catalyst used in the invention (VII). (A) The metal palladium, the group (b) compound, and the group (c) element loading relative to the carrier are the same as those used in the invention (VII). The catalyst is the same. (D) The loading amount of the group elements with respect to the carrier will vary depending on the particle size and pore structure of the carrier, but it is preferably between 0.000 and 1 with respect to the carrier. -3.0% by weight, more preferably in the range of 001_2% by weight. Herein, "% by weight" refers to the proportion of the weight of group (d) elements in the catalyst relative to the weight of the carrier. This paper size applies China National Standard (CNS) A4 (21〇X 297 public love) 40

i.l -------- -------- (Please read the notes on the back before filling this page) 491835 Α7 Β7

Printing of clothing by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (38) A method such as Invention (XI) will now be described, which is used to manufacture the non-invention of any one of Inventions (VI) to (IX). Supported fixed catalyst. Invention = XI) method is a method for producing a non-supported fixed catalyst, which is used to produce acetic acid and acetic acid as in any of inventions (VI), (νπ), (VIII) or (Ιχ) Ethyl ester. The manufacturing method (1) of the invention (XI) is a method for manufacturing the catalyst of the invention (VI), and includes the following first and second steps. Step 1 is a step in which a palladium suspension is prepared. The second step is a step in which (b) at least one compound selected from the group consisting of: · an inorganic acid and a salt thereof is dissolved or suspended in the babarium suspension solution prepared in the first step, and then the solvent Removed. The first step of the manufacturing method (1) of the invention (XI) is a step in which a palladium suspension is prepared. In the production method (1) of the invention (XI), there is no particular limitation on the compound which is the starting material of the metal palladium. Generally, compounds which can be converted into metal handles are used, including halides such as gasification handles, organic acid salts such as acetic acid handles, but also nitric acid handles, oxidized acid salts, sulfuric acid handles, and sodium tetrakidronate, and the metal itself. Suspensions of palladium can be prepared by dissolving or suspending the starting compound of metallic palladium in a suitable solvent. The solvent used here can be water or an inorganic or organic solvent such as acrylic paper. Applicable to China National Standard (CNS) A4 (210 X 297 mm). 41 ------------- -------- Order --------- line (please read the precautions on the back before filling this page) 491835

V. Description of the invention (39) Ketoethanol, etc., printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, may be dissolved in an inorganic or organic acid such as hydrogen acid, nitric acid or acetic acid in the solvent used if necessary. The starting compound of metal palladium is preferably one which can be uniformly dissolved or suspended by stirring or the like, but there is no particular limitation on it. If necessary, the metal fume starting compound may also be subjected to a reduction treatment 'to convert it into a metal handle. In the case of the reduction treatment in the first step, the effect of converting the metal palladium starting compound that can be converted into metal palladium into metal palladium is not particularly limited. In more detail, a method may be mentioned in which the metal palladium starting compound is reduced to metal palladium with a suitable reducing agent such as hydrazine, formaldehyde solution, A, methanol, ethylene, hydrogen, and the like. The reduction treatment can be carried out in the liquid phase state. The liquid phase reduction treatment is generally performed at room temperature, but it can also be performed by heating to a higher temperature, for example, about 30-50 c. The gas-phase reduction treatment is preferably carried out by heating to about 100-600 (rc) to completely convert to metal. In this way, a palladium suspension can be prepared. As in the second step of the production method (XI) of the invention (XI), A step in which (b) at least one compound selected from the group consisting of: an inorganic acid and a salt thereof are dissolved or suspended in a hydrazone floating liquid prepared in step 1, and then the solvent is removed to obtain a The catalyst used to make acetic acid and ethyl acetate. The compound of group (b) used in this step is the same as the catalyst used in invention (VI). A method for dissolving or suspending the inorganic acid or its salt, It is a method that can produce homogeneity by stirring the ingredients, and there is no special paper rule for it & use Chinese National Standard (CNS) A4 specification (21_0 x 297 public love) ------ ---- —: ---- 丨; -----—------- ^ 丨 Order -------- line ^^ (Please read the precautions on the back before filling in this Page) 491835 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-V. Description of the invention (40 limitation. Example h 'Right 1¾ Inorganic acids or their salts are soluble I, which can be directly dissolved in Ji In the suspension solution, if it is not a combination, it is possible to adopt a method to suspend the inorganic meaning or its salt in a suitable, cross-linked formula from $ 'X' Vc »k and / mixture Then, the palladium suspension solution is added dropwise. There is no particular limitation on the method for removing the solvent, and it can be any well-known method such as heating, decompression, etc. In the case of heating, 'this The temperature is preferably a temperature that does not cause decomposition of the inorganic acid. Especially in the case of heteropolyacids, if the temperature is higher than that, decomposition may occur: and it may impair the activity and activity of the catalyst produced by this method. Selectivity. In the second step, if it needs to be converted into a metal handle, the starting compound of the metal handle can also be subjected to reduction treatment. In the case of the reduction treatment in the second step, the metal palladium that can be converted into metal palladium is also about to be converted. The effect of the conversion of the starting compound into metallic palladium is not particularly limited to the method used. In more detail, a method may be mentioned in which the metal Iε starting compound is a fine reducing agent such as hydrazine, formaldehyde Liquid, nitrogen, methanol, ethylene Hydrogen, etc., and reduced to metal palladium. The reduction treatment can be performed in the liquid or gas phase. The liquid phase reduction treatment is usually performed at room temperature, but it can also be performed by heating to a higher temperature, such as about 30-5 {rc. The gas-phase reduction treatment is preferably carried out by heating to about 100-600 C to completely convert to a metal. The method for converting a metal palladium starting compound that can be converted into metal palladium into a metal can be used at the time A metal palladium starting compound containing (b) at least one compound selected from the group consisting of inorganic acids and their salts is in suspension --- Order--I--I --- line (please read the notes on the back before filling this page) Printed by A7, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ---- ^ ____ V. Invention Description (41 ) In liquid state, or after separation. The catalyst of the invention (VI) can be prepared in the manner described above. The production method will now explain the manufacturing method (2) such as the invention (XI). The manufacturing method (2) of the invention (XI) is a method for preparing a catalyst such as the invention (VII), and includes the 2nd step of the manufacturing method (1) of the invention (XI), And including a third step in which at least one element selected from the group consisting of elements of groups 14, 15, and 16 of the periodic table is added to one or both of these steps. The starting compound of the ytterbium metal handle used in step j of the method and its / composition or suspension method are the same as those in the method (1) for producing the catalyst for the invention (VI) as in the invention (χι). 1 steps are the same. There is no particular limitation on the starting material of the group (C) element, and it may be 7G element itself or a functional compound, nitrate, acetate, salt filler, sulfate or oxide containing the element, or even It is a complex having an organic molecule such as acetoacetone or nitrile as a ligand. In more detail, mention may be made of gaseous compounds such as gaseous selenium, gaseous pounds, gaseous antimony, gaseous tin, gaseous bismuth, gaseous lead, etc .; nitrates such as antimony nitrate, lysin, bismuth nitrate 'nitric acid Lead, etc .; Acetates such as tin acetate, bismuth acetate, lead acetate, etc .; and selenium oxide, selenic acid (H2se04) and its salts, selenite (HdeO3) and its salts, metal selenium, pound oxide, pound acid ( H6Te〇6) and its salts, HjeO3 and its salts, metal pounds, potassium antimonate, etc., but not limited to these substances. When adding the group element in step 1, it is used to dissolve or suspend. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love). 44

-11 ^ -II .1 ------- Γ -------- (Please read the notes on the back before filling out this page) 491835 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

A7 ------- B7 -------- 、 Explanation of the invention (42) The method of the starting compound of group (C) elements can generate the starting compound with metal palladium by stirring or the like Any method of uniformity is not particularly limited. For example, if it is soluble, it can be dissolved directly with the starting compound of metal palladium. If it is not soluble, a method can be used to suspend the starting compound of group (C) elements in a suitable solvent. Then, the resulting solution is added dropwise to a solution in which the metal palladium starting compound has been dissolved or suspended. The solvent used herein may be water or an inorganic or organic solvent such as acetone, ethanol, etc., and an inorganic or organic acid such as hydrogen acid, nitric acid or acetic acid may be dissolved in the solvent used if necessary. The starting compound of the group (c) is preferably one which can be uniformly dissolved or suspended by stirring or the like, but it is not particularly limited. In the first step, a method for converting a metal palladium starting compound that can be converted into metal palladium into metal palladium, that is, a reduction treatment method, is the i-th step as in the manufacturing method (1) of the invention (XI) The steps are the same. A palladium suspension can be obtained in the manner described above. The compound of group (b) used in step 2 is the same as the catalyst used in the invention (VI), and the method of dissolving or suspending the compound of group (b) and the method for removing the solvent are the same as those of the invention ( The second step of the manufacturing method (1) of X1) is the same. When the (c) group element is added in the second step, the starting compound of the element and the method for dissolving or suspending the starting compound of the (c) group element may be the same as the manufacturing method of the invention (XI) (2 Step i) is the same. This paper size is applicable to Zhongguanjia Standard (CNS) A4 size (Q χ Noragei)

— II — — — — — — — · 11 (Please read the notes on the back before filling this page) 1 ^ · -line. 45 491835

There is no particular restriction on the order in which the compounds of group (b) and the elements of group (c) are added to the palladium suspension, and two or more of them may be added simultaneously or in any desired order. That is, the group 同时 compound and the group 元素 element may be added at the same time or the group (c) group element may be added separately before adding the group (b) compound. In the second step, a method for converting a metal palladium starting compound that can be converted into metal palladium into metal palladium, that is, a reduction treatment method, is the second step from the manufacturing method (丨) of the invention (XI) The steps are the same. The catalyst of the invention (VII) can be obtained in the manner described above. The manufacturing method (3) such as the invention (XI) will now be explained. The manufacturing method (3) such as the invention (χι) is a method for manufacturing a catalyst such as the invention (νιπ), and includes the i-th and second steps of the manufacturing method (1) such as the invention (XI), and Include a third step in which one or both of these steps are added (❼ at least one element selected from the group consisting of elements of groups 6, 7, 8, 9, ι0, 11 and 12 of the periodic table. The (a) starting compound of metal palladium used in the first step of the method and the method for dissolving or suspending it are the same as the i-th step of the production method (1) of the invention (χι). For the group (d) The starting material of the element is not particularly limited, and it may be the element itself or a halide, nitrate, acetate, phosphate, sulfate, or oxide containing the element, or even an organic molecule such as acetic acid A complex of acetone or nitrile as a ligand. In more detail, chlorides such as chromium chloride, gasified manganese, gasified baht, gasified ruthenium, rhodium chloride, gasified iridium, gasified Nickel, tetrachloroaurate and its salts, zinc chloride and its salts Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) ------- Γ -------- Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative 46 491835 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Chromium, manganese acetate, baht acetate, ruthenium acetate, iridium acetate, nickel acetate, zinc acetate, etc .; but it is not limited to these substances. Although the group (d) element is added in step 1, it is used to dissolve or suspend the ( d) The method of the starting compound of the group of elements is any method that can produce homogeneity with the metal palladium starting compound by stirring, etc., and there is a special limitation on its co-production. For example, if it is soluble Alternatively, it can be directly dissolved with the starting compound of metal palladium. If it is not soluble, a method can be adopted to suspend the starting compound of group (d) elements in a suitable solvent, and then the resulting > Valley liquid is added dropwise to the metal to dissolve the starting compound Or suspended in one of the solutions. The solvent used herein may be water or an inorganic or organic solvent such as propyl alcohol. If necessary, an inorganic or organic acid such as hydrogen acid, may be dissolved in the solvent used. Nitric acid or acetic acid. The starting compound of the element of group (d) is preferably one that can be uniformly dissolved or suspended by stirring or the like, but there is no particular limitation thereon. When used in the first step, The method for converting the metal palladium starting compound converted into metal palladium into metal palladium, that is, the reduction treatment method, is the same as the first step of the manufacturing method (1) of the invention (XI). Palladium can be obtained in the manner described above. Suspension. The compound of group (b) used in step 2 is the same as the catalyst used in the invention (VI), and the method of dissolving or suspending the compound of group (b) and the method for removing the solvent are the same Such as the invention (χι) of the catalyst used for invention (VI) Paper size_Chinese National Standard (CNS) A4 χ tear public love) 47 -------- Order --------- line (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 491835 A7 ------------ B7__ 5. The second step of the manufacturing method (1) of the invention description (45) is the same.添加 In the second step, when adding a group element, the starting compound of the element and the method for dissolving or suspending the starting compound of the group (d) element may be the same as the first step of the manufacturing method (3). There is no particular limitation on the order in which the (b) group of compounds and the (d) group of elements are added to the palladium suspension, and two or more of them may be added simultaneously or in any desired order. That is, they may be added simultaneously ( Group b) and group (d) elements, or add group (b) elements separately before adding group (b) compounds. When in the second step, the metal palladium starting compound that can be converted into metal palladium is converted The method for metal palladium, that is, the reduction treatment method, is the same as the second step of the manufacturing method (丨) of the invention (XI). The catalyst of the invention (νιπ) can be prepared in the manner described above. The invention will now be described The manufacturing method (4) of (XI). The manufacturing method (4) of the invention (χι) is a method for manufacturing the catalyst of the invention (IX), and includes the manufacturing method of the invention (XI) (1) ) Of steps i and 2 and including step 3 In which at least one element selected from the following group is added to one or both of these steps: elements of groups 14, 15, and 16 of the periodic table and (d) at least one element selected from the group: period The elements of Groups 6, &, 9, 10, 11 and 12 of the table. (A) The starting compound of metal palladium used in the first step of the method and the method for dissolving or suspending the same are as described in the invention (XI) The manufacturing method of step ^ is the same. (C) The starting materials of the elements of the group and the means for dissolving and suspending them (Please read the precautions on the back before filling this page) ----- --- --------

• V. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 The invention description (46) is the same as step i of the manufacturing method (2) of the invention (XI). The starting material of the group (d) element and the method for dissolving and suspending it are the same as the first step of the manufacturing method (3) of the invention (XI). In the first step, the method for converting a metal that can be converted into a metal handle to a starting compound into a metal handle, that is, a reduction treatment method, is the first step as in the manufacturing method (1) of the invention (XI) The steps are the same. A palladium suspension can be obtained in the manner described above. The compound of group (b) used in step 2 is the same as the catalyst used in the invention (VI), and the method of dissolving or suspending the compound of group (b) and the method for removing the solvent are the same as those of the invention ( XI) The second step of the method (1) for producing the catalyst used in the invention (VI) is the same. When a group VIII element is added in the second step, the starting compound of the element and the method for dissolving or suspending the starting compound of the group (c) element can be used in the same way as the invention (XI) for the invention (VII) The first step of the catalyst manufacturing method (2) is the same. When group (d) element is added in the second step, the starting compound of the element and the method for dissolving or suspending the starting compound of group (d) element can be used in the same way as invention (XI) for the invention ( The first step of the method (3) for producing the catalyst of VIII) is the same. There is no particular restriction on the order in which the (b) group of compounds and / or (C) group of elements and / or (d) group of elements are added to the palladium suspension, two or more of them may be added at the same time or any desired Add in order. That is, group (b) compounds, group (c) elements and group (d) elements can be added at the same time, or they can be added simultaneously or separately (b) This paper size applies the Chinese National Standard (CNS) A4 specification (21〇X 297 Public Love) ^ -------- ^ --------- ^ (Please read the notes on the back before filling out this page) 49 491835 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention The compound of the group (47) and the element of the group (c), and then a suspension containing one of the compound of the group (b) and the element of the group (c) can be prepared, and the element of the group (d) is added. In the second step, a method for converting a metal palladium starting compound that can be converted into metal palladium into metal palladium, that is, a reduction treatment method, is the second step from the manufacturing method (1) of the invention (XI) The steps are the same. The catalyst of the invention (IX) can be obtained in the manner described above. A method for producing a carrier-fixed catalyst of the invention (X) as the invention (XY) will now be explained. The method of invention (XII) is a method for producing a carrier-fixed catalyst such as that of invention (X) for producing acetic acid and ethyl acetate. A method for manufacturing a carrier-fixed catalyst of the invention (X), such as the invention (XII), includes the following first and second steps. The first step is a step in which 0) metal palladium is packed on a support to obtain a catalyst filled with metal palladium. The second step 'system-step' wherein at least one compound selected from the group consisting of inorganic acids and salts thereof is loaded on a metal-palladium-filled catalyst prepared in the first step to obtain- Catalyst for the manufacture of acetic acid and ethyl acetate. In the manufacturing method (1) of the invention (XII)! In the step, the catalyst is packed on a carrier to obtain a catalyst packed with metal sharp. The metal palladium starting compound used in the first step is the same as the invention (χι) 'paper size applies Chinese National Standard (CNS) A4 specifications (21〇χ 297 mm-IT ------- r I -------- (Please read the precautions on the back before filling out this page) 50 • Five, the first step of the manufacturing method (1) of the invention description (48) is the same. There is no particular limitation on the method for loading the metal-based metal starting compound on the carrier, and it can be filled by any method. For example, when loading a metal palladium starting compound that can be converted into metal palladium, the The metal palladium starting compound is dissolved or suspended in a suitable solvent such as water or propylene, an inorganic or organic acid such as chlorochlorohydrazone, acetic acid, etc., or a mixture thereof, and then it is loaded on a carrier and applied. The method of drying and preparing the material on the carrier. For the light filling method, the dipping method, the method of evaporation to dryness, the kneading method and the spraying method can also be mentioned, but it is not limited to these methods. When filling When a metal palladium starting compound can be converted into metal palladium, The method for converting a metal starting compound into a metal hafnium is not particularly limited. The method of the original treatment is not limited. The reduction treatment may be performed in a liquid phase or a milk phase as long as these conditions are general reducing conditions, and there is no special Limitation. Liquid phase reduction treatment is generally performed at room temperature, but it can also be performed by heating to a higher temperature, such as about 30-5 generations. Gas phase reduction treatment will heat the metal to the starting compound to about Rigid-cap. C to perform 'to complete conversion to palladium metal. In more detail, a method may be mentioned, which will be directly or treated with an aqueous solution of sodium hydroxide, barium hydroxide, sodium metalite, etc. After the compounds are converted into oxides, hydroxides, etc., the starting compounds are reduced to metals by hydrazine, methylphenidate, hydrogen 'methanol, ethylene, etc. It is used to convert metals that can be converted into metals. Conversion of Metallic Starting Compounds A7 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

\ ------- Γ -------- $ I (Please read the notes on the back before filling this page) ------ -___ B7 —____ V. Description of the invention (49) The method of palladium may be performed after separating the catalyst containing the metal palladium starting compound, or may be performed immediately after the charging method. If possible, it is preferably performed immediately after the filling method without separation. If necessary, the catalyst filled with metal palladium can then be filtered by a general method, and then washed and dried to remove any substances that inhibit the catalytic reaction, such as alkaline compounds of sodium hydroxide or sodium. A catalyst filled with metal palladium can be obtained in the manner described above. In the second step of the production method (XII), the metal palladium-filled catalyst obtained in the first step is charged with (b) at least one compound selected from the following group: inorganic acid And its salts to prepare the catalyst of invention (X). In the second step, the compounds of group (1)) are the same as those used for the catalyst of the invention (νι). There is no particular limitation on the method of filling the group VIII compound, and the filling effect can be performed by any method known to the public. In detail, mention may be made of methods such as immersion method, spray concentration method,? The method of bursting to dryness, kneading method and adsorption method is not limited to these methods. The solvent used for the impregnation method may be any soluble inorganic acid, and water, organic solvents, and mixtures thereof may be used. Preferably, water or alcohol is used. In the manner described above, a catalyst such as the invention (x) can be obtained. For example, the invention (XI1) manufacturing method (2) for manufacturing the carrier-fixed catalyst of the invention (X) includes one or both of steps 1 and 2 of the manufacturing method (1) of the invention (XII) Add at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table. This paper scales the standard + CNS A4 specification (⑵〇 X 297) 52 491835 A7 B7 • Five, the description of the invention (50 objects and = manufacturing method (2) the first step of the metal handle The method of initiating chemical compound ... filling and converting to metal saturation is the same as the first step of the method (1) of the invention of the clothes of the gangue. When the elementary group of elementary group is added in step 1, the elementary group of elementary group of elementary group It is the same as the first step of the manufacturing method (2) of the invention (XI).-There is no particular limitation on the method for loading the starting compound of the element VIII group on the carrier, and the loading effect can be arbitrary -The method is complete. For example, the starting compounds of the elements of the amidine group are soluble in a suitable: agent such as water or propane, soluble in an inorganic or organic acid such as hydrochloric acid, nitric acid, etc. Dipping into the carrier and drying it as a method of filling on the carrier. The ordering and filling method can be any one of the methods such as the dipping method, the method of sending to the dry side, the kneading method and the spray concentration method. Method, but is not limited to these methods. The effect of filling on the carrier and the effect of filling the starting compound of group (0) elements on the carrier can be performed in the order of any Γ. That is, the two loading effects can be performed simultaneously, or one after the other.仃. The starting compound of group (C) element and the starting compound of (a) metal palladium are packed on the carrier on the same day, which is the better and the most common. The catalytic side filled with palladium metal is filtered by a general method, and then washed and dried to remove any substance that inhibits the catalytic reaction, such as a dentate or an alkaline salt of sodium, etc. A metal filled with the metal can be prepared in the above manner. Catalyst for palladium. In the second step, the compounds of group (1)) and their filling methods are in accordance with the standard (CNS) A4 size of paper issued by JP 297 (Public Love) 491835 A7.

II Please read the notes on the back before filling this page. 5. Description of the Invention (52) Method and Spraying Two Methods such as dipping, kneading to dry, kneading, and / or one method, but not limited to these methods. . The effect of loading the starting compound of rhenium metal palladium on the carrier and the effect of loading the cis = starting compound on the carrier can be performed at the same time according to any of the -n loading effects, or -the predecessor-to-descendant: The starting compounds of the group elements and the initial metallurgical metallization are loaded on the carrier, which are the better and most common ones. On the right, it can be cleaned and dried after being filled with the metal squeegee 1 by ordinary methods to remove any substances that inhibit the catalytic reaction, such as alkaline compounds such as compounds or sodium. According to the method, _ kinds of catalysts filled with metal handles can be prepared. The second step is to select at least one chemical compound selected from the group: inorganic acids and their salts and / or at least one selected from the following groups: Periodic table m9, i The 70 element 'of u, u and ⑽ was packed in the metal-filled catalyst prepared in the first step to prepare the catalyst of the invention (X). In the second step, the compounds of the group "⑻" and the method for filling the same are the same as the second step of the production method 如 of the invention (XΠ). When the element VIII group is added in the second step, the starting compound of the group VIII element is the same as the first step of the manufacturing method (3). The loading of the same hafnium compound on a catalyst loaded with metal palladium and the starting compound of a hafnium group element on a metal-filled catalyst can be performed in any order. That is, the two filling functions can be printed on a paper rule ^ Caiguan Jiaxian (CNS) A4 ^^ 297 mm) 491835 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of Inventions The process is performed in the following manner. The catalyst such as the invention (X) can be prepared in the manner described above. The method (4) for manufacturing the carrier-fixed catalyst for the invention (χ) as the invention (XII) is a kind of The method for producing the catalyst of invention (IV). It can be added to one or both of the first and second steps of the production method of invention (XII) (at least one element selected from the following group ...) Week / Month table Groups 15, 15 and 16 elements and (d) at least one element selected from the following groups · Periodic table elements 6, 7, 8, 9, 10, 11 and 12 and manufactured The catalyst of invention (IV) In the manufacturing method (4), the starting material of the metal palladium used in the first step (a) and the method of filling or converting it into the metal age are related to the invention (XII) The manufacturing method (1) is the same as the first step. When group (e) is added in the first step, (the initial combination of the elements of the magic group) And its filling method are the same as the first step of the manufacturing method (2) of the invention (χπ). When the group (d) element is added, the starting compound of the group (d) element and its loading method are the same as the invention ( Step 丨 of the manufacturing method (3) of χΠ) is the same. The effect of loading (a) the starting compound of metal palladium on the carrier, the loading of the starting compound of group (c) elements on the carrier, and / Alternatively, the effect of loading the starting compound of the element of group (d) on the carrier may be performed in any order. That is, the three loading effects may be performed simultaneously or one after the other. (C) Group The loading of the starting compound of the elementary compound and the starting compound of the element of the group (d) on the carrier is performed simultaneously with the starting compound of the (a) metal palladium. The paper size applies the Chinese National Standard (CNS) A4 specification (21G X 297 public love i Γ ------- order -------- line '(Please read the precautions on the back before filling out this page) -V. Invention description (54) is better and most common It should be possible to filter the catalyst filled with metal palladium by ordinary methods, post / monthly washing and drying to remove any Manufactured by catalytic reaction of the substance, a basic salt such as sodium halide or the like of the above-described embodiment can be obtained I _ recorded heart filled with a catalyst of gold. -.

The second step of the clothing method (4) is performed by selecting (b) at least one compound selected from the group consisting of: inorganic acids and their salts, and at least one element selected from the group consisting of: periodic table Elements from Groups 14, 15 and 16 and / or ⑷ to) An element selected from the group consisting of Periodic Table 6, 7, 8, 9, 10, 'Private elements, filled in the first step The obtained catalyst loaded with metal palladium was used to prepare the catalyst of the invention (X). In the second step, the group VIII compound and its filling method are the same as the second step of the production method (XII). When the element of the group VIII is charged in the second step, the starting compound of the group VIII element and the method of filling the same are the same as the step [1] of the manufacturing method (2) of the invention (XII). When the group 元素 element is loaded in the second step, the starting compound of the group 元素 element and its filling method are the same as those of the manufacturing method of the invention (χιι)! The steps are the same. In the second step, the group ⑻ compounds are filled with metal! The loading effect on the catalyst of Ba and / or the starting compound of the element VIII and / or the starting compound of the element VIII can be performed in any order according to the loading effect on the metal catalyst. That is, these filling effects can be performed simultaneously, or 491835 A7

-II I --- i —Order · ---- ί ·· * ^ ·· (Please read the notes on the back before filling out this page) B7 、 Invention Note (56) (Please read the notes on the back first Please fill in this page again) The reaction temperature of alcohol and oxygen in the gas phase is not particularly limited, but it is preferably 100-25 ～ (. If the reaction temperature is lower than 10.0, it will cause Insufficient reaction rate. If the reaction temperature is higher than 250 ° C, a large number of secondary reactions will tend to occur. In terms of application, 'more preferably is in the range of 120-230 ° C. As far as the equipment is concerned, The application pressure is from 00 to 30 MPa (gauge pressure) is advantageous, and more preferably ranges from 01 to 1.5 MPa (gauge pressure). In the case of flow-type reactions, supply The gas to the reaction system includes ethanol and oxygen, and if necessary, nitrogen, carbon dioxide, rare gases, etc. can be used as diluents. The amount of ethanol supplied to the reaction system corresponds to 0.1-50% by volume of the total gas supplied The proportion of oxygen, especially 0.5-5 vol%, the amount of oxygen corresponds to the proportion of 1-15 vol%, especially 2-1 〇 %. Here, a higher ethanol concentration in the supply gas will cause more ethyl acetate to be produced, while a lower concentration will cause selective selectivity to acetic acid. If the ethanol concentration exceeds 50% by volume, Will tend to increase the number of secondary reactions, on the other hand, if the ethanol concentration is less than 0.1% by volume, it will tend to reduce productivity. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, the consumer cooperative, printed in the reaction system, will provide enhanced acetic acid It has significant effects on the activity and selectivity with ethyl acetate, and prolongs the activity of the catalyst in the reaction system. It is suitable to include 0.1-50% by volume of water vapor in the reaction gas. If the water in the reaction gas is suitable If the steam system is present in an amount of less than 0.1 volume by 0/0, the catalyst may degrade more quickly. If the steam system is present in an amount of more than 50% by volume, the demand for the steam device may be poor. In terms of application 59 paper size Applicable to China National Standard (CNS) A4 (210 X 297 mm) A7 A7

5. Description of the invention (57), the range is preferably 0.5-40% by volume. (Please read the notes on the back before filling this page.) When the invention (χιπ) method is carried out by this gas phase reaction, it is advantageous to use 鬲 purity ethanol starting material, but if a small amount of low grade is added Saturated hydrocarbons such as methane, ethane or propane, or acetaldehyde, diethyl ether, acetone, are not a problem. In more detail, acetaldehyde, diethyl ether, ethylene and the like as trace by-products of the reaction can be converted into acetic acid and / or ethyl acetate by the catalyst of the present invention. Oxygen can also be in the form of air and diluted with a U-type gas such as nitrogen or carbon monoxide. However, when 4 reaction gas k is circulated, the concentration of oxygen is generally more favorable, preferably more than 99%. The volume velocity of the reaction mixed gas passing through the catalyst is preferably in the range of 500-15,000 hours-1, especially in the range of 1000-10,000 hours-1, under standard conditions. Next, a liquid phase reaction will be explained. In the manufacturing method of acetic acid and ethyl acetate produced by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as invented (XIII), there is no particular limitation on the reaction temperature of ethanol and oxygen in the liquid phase, but it is preferably 0- 200 ° C. If the reaction temperature is lower than 0 ° C, the reaction rate will be insufficient. If the reaction temperature is lower than 200 ° C, a large number of secondary reactions may occur. In terms of application, it is more preferably in the range of 20-110 ° C. In terms of equipment, the reaction pressure is actually advantageous from 0.0 to 3.0 MPa (gauge pressure). More preferably, it is in the range of 0.1 to 1.5 MPa (gauge pressure). Ethanol and / or oxygen starting materials may be present in the catalyst beforehand, or added at appropriate points in the reaction. It can be supplied to gas-phase or liquid-phase to the 60th paper size applicable to China National Standard (CNS) A4 (210 X 297 mm)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of Invention (58)-It should be in the system. The starting materials supplied to the reaction system include ethanol and oxygen, and gas, carbon monoxide, or a diluent gas may also be used. If water is present in the reaction system, it will provide a significant effect to enhance the activity and selectivity of acetic acid and ethyl acetate production, and prolong the activity of the catalyst in the reaction system. There is no particular limitation on the ratio of water to ethanol in the reaction system. During the reaction, even the ratio of water to ethanol may be changed, or a suitable amount of water may be added to maintain a constant ratio. If necessary, an experimental component such as sodium hydroxide may be added to increase the reaction rate. When the invention (XII) is carried out by this liquid phase reaction, it is advantageous to use a high-purity ethanol starting material, but if a small amount of a lower saturated hydrocarbon such as methane, ethane or propane, or acetaldehyde is incorporated , Diethyl ether, ethylene, etc. 'will not pose a problem. In more detail, the trace by-products of the reaction, ethyl alcohol, diethyl ether, ethylene, etc., can be converted into acetic acid and / or ethyl acetate by the catalyst of the present invention. Oxygen can also be in the form of air and diluted with an inert gas such as nitrogen or carbon dioxide. However, when the reaction gas is circulated, it is generally advantageous to use a high concentration of oxygen, preferably more than 99/0. In this way, the effect of producing acetic acid and ethyl acetate, such as invention (XIII), can be used to produce acetic acid and ethyl acetate from ethanol and oxygen to the south. The obtained acetic acid and ethyl acetate can be separated and purified to a desired purity by a general method. When unreacted starting materials and by-products such as acetaldehyde and / or diethyl ether are retained, the unreacted starting materials and by-products such as acetaldehyde and / or diethyl ether can be recovered to the reaction system The paper size for use in this paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 61 -------- 1 --------- line (please read the precautions on the back first) (Fill in this page again) 4 ^ 1835 V. Description of the Invention (59) Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Printing Co., Ltd. When industrial applications require acetic acid or ethyl acetate, they can be removed and removed after the reaction to obtain The desired substance, another product will be returned to the reaction system. For example, if ethyl acetate is needed, the ethyl acetate is separated and recovered after the reaction. @Acetic acid will be returned to the reaction system to obtain additional ethyl acetate from acetic acid and ethanol. When needed ', the catalyst used can be regenerated at a suitable point in time or separated for reuse. The present invention will now be described in detail by the following examples, which are provided only for the general description of the present invention and are not intended to limit the present invention in any way. All the carriers used in the following examples were dried in air for 4 hours as a pretreatment. The water used in the examples is deionized water. The first handle was added with silicon oxide in an aqueous solution (45 ml) of sodium tetrachloride [Na2PdCl4, product of Takana Kikinzoku] (1.90 g) and acid [H6Te06, product of Kanto Chemical Co., Ltd.] (0 13 g). Carrier [KA_i, particle size: 5 mm p, product of Zud-chemie AG] (69 g) to absorb the entire amount. Then, it was added to an aqueous solution (100 ml) of sodium metasilicate nonahydrate [Na2Si〇3 • 9H20, product of Wako Junyaku] (5.5 g), and the mixture was allowed to stand at room temperature for 20 hours. Then add hydrazine monohydrate [N2H4 · H20, product of Wako Junyaku company] (5g) This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 62 -------- ------------- Order --------- Line (Please read the precautions on the back before filling out this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491835 A7- ------- B7 V. Description of the invention (60): and gently stir, and let the mixture stand at room temperature for 4 hours to reduce to metal palladium. After the catalyst was filtered and decanted, it was transposed. It was placed in a glass column equipped with a cock, and purified water was passed at a rate of 1.5 liters per hour for 40 hours for cleaning. It was then dried under an air flow of 110 ° C for 4 hours to prepare the first catalyst for the production of acetic acid. k In the second example, except that lead acetate trihydrate [(CH3COO) 2Pb · 3H20, a product of Wako Junyaku]] (0.74 g) was used in place of the acid in the first example, the same method as in the first example was used to prepare A second catalyst for producing acetic acid was obtained. The third example was added to an aqueous solution (45 ml) of sodium tetrakisdium (1.90 g) in an aqueous solution (KA -1 'particle size · 5¾ mφ, product of Zud-chemie AG) (69 g) To absorb the full amount. This was then added to an aqueous solution (100 ml) of sodium metasilicate nonahydrate (5.5 g), and the mixed poplar was allowed to stand at room temperature for 20 hours. Then add hydrazine monohydrate (5 g) and gently stir it 'and let the mixture stand at room temperature for 4 hours to reduce to metal princess. After the catalyst was filtered and decanted, it was transferred to a glass column equipped with a cock, and purified water was passed at a rate of 15 liters per hour for 40 hours for cleaning. Then, it was dried for 4 hours under a gas flow of 11 ° C to prepare a catalyst filled with metal palladium. Then add the catalyst filled with metal palladium to sodium aloate. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 63 -------------- pack- ------- Order --------- line (please read the notes on the back before filling this page) 491835 A7 ______ V. Description of the invention (61) (Please read the notes on the back before (Fill in this page) [Na2Te03, a product of Wako Junyaku Chemical Co., Ltd.] (0.12 g) in an aqueous solution (45 liters) to absorb the entire amount. Then at 110. (: It is dried for 4 hours under an air stream to prepare a third catalyst for producing acetic acid. The fourth example is except for bismuth nitrate pentahydrate [Bi (N03) 2 · 5H20, a product of Wako Junyaku]] (〇 · 37 g) of an acetic acid solution was used in place of the sodium bisulfite in the third example, and a fourth catalyst for the production of acetic acid was prepared in the same manner as in the third example. The fifth example except for tin acetate [(CH3COO) 2Sn, a product of Wako Junyaku Company] (0.26 g) of acetic acid solution was used in place of sodium pound sulfite in the third example, and the $ th catalyst for producing acetic acid was prepared by the same method as in the third example. The sixth case was printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in an aqueous solution (56 liters) of sodium tetrakidronate (1.90 g), and a silicon oxide carrier was added [0081 ^ 八 (: 丁, (5-10卩 1 ^ 8gawa (product of Chemical Co., Ltd.) (57 g) to absorb the entire amount. Then it was added to an aqueous solution (100 ml) of sodium metasilicate nonahydrate (6.0 g), Allow the mixture to stand at room temperature for 20 hours. Then add hydrazine monohydrate (5 g) and stir gently to allow the mixture at room temperature It was allowed to stand for 4 hours to reduce to metal palladium. After filtering the catalyst and decanting, it was transferred to a glass column equipped with a cock and passed through the purified product at a rate of 1.5 litres per hour. Water for 40 hours for cleaning. Then dried under an air flow of 110 ° C for 4 hours to obtain a metal-filled catalyst. 64 This paper is sized to Chinese National Standard (CNS) A4 (210 X 297 issued) ^ 1835 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed on the description of the invention (62) Then the catalyst filled with metal was added to an aqueous solution of sodium hypothionite (ο. 12 g) (55 ml ) To absorb the entire amount. Then, it was dried under a gas flow of U0 ° C for 4 hours to prepare a sixth catalyst for the production of acetic acid. The seventh example was an aqueous solution of sodium tetrachloropalladate (1.90 g) (42 ）), Add a titanium oxide support [CS-300S-46, particle size: 3-5 mm φ, a product of Sakai Chemical Industry Co., Ltd.] (107 g) to absorb the entire amount. Then add it to the metasilicon Sodium Nine Hydrate (6.0 g) The solution (100 ml) was allowed to stand at room temperature for 20 hours. Then hydrazine monohydrate (5 g) was added and gently stirred, and the mixture was allowed to stand at room temperature for 4 hours to reduce to Metal palladium. After filtering the catalyst and decanting it, it was transferred to a glass column equipped with a cock and passed through purified water at a rate of 1.5 liters per hour for 40 hours for cleaning. Then, it was dried under an air flow of 110 ° C for 4 hours to prepare a catalyst filled with metal palladium. The catalyst filled with the metal was then added to an aqueous solution (42 ml) of sodium albino (0.12 g) to absorb the entire amount. Then, it was dried for 4 hours under a stream of 丨] ^^ to prepare a seventh catalyst for producing acetic acid. The eighth example was added silica (45 ml) to an aqueous solution (45 ml) of sodium tetrachlorate (1.90 g) and tetrakisauric acid tetrahydrate [H4AuCl4 • 4H20, product of Takana Kikinzoku] (0.50 g). Carrier [KAq, particle size: 5 mm $, product of Zud-chemie AG] (69 g) to absorb the entire amount. This paper size applies to China National Standard (CNS) A4 specification (21 × 297 public love) ------------- Installation -------- Order ------- --Line (please read the notes on the back before filling out this page) 65 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491835 A7 B7 V. Description of Invention (63) Then add it to sodium metasilicate nonahydrate ( 6.9 g) of an aqueous solution (100 ml), and the mixture was allowed to stand at room temperature for 20 hours. Then hydrazine monohydrate (6.5 g) was added and gently stirred, and the mixture was allowed to stand at room temperature for 4 hours to reduce to metal palladium. After the catalyst was filtered and decanted, it was transferred to a glass column equipped with a cock, and purified water was passed at a rate of 1.5 liters per hour for 40 hours for cleaning. Then, it was dried under an air flow of 110 ° C for 4 hours to prepare an eighth catalyst for producing acetic acid. The ninth example was prepared in the same manner as in the eighth example except that the tetrachloroauric acid tetrahydrate of the eighth example was replaced with zinc gas [ZnCl2, a product of Wako Junyaku Company] (0.08 g). Ninth catalyst for producing acetic acid. The tenth example was replaced by the gasified chromium hexahydrate [CrCl3 · 6H20, a product of Wako Junyaku] (0.22 g) in the eighth example, and the same method as in the eighth example was used. The 10th catalyst used to produce acetic acid was prepared. The eleventh example was replaced by the gasified fibrous tetrahydrate [MnCl2 · 4H20, a product of Wako Junyaku] (0.22 g) in the eighth example, by the same method as in the eighth example An eleventh catalyst was prepared to produce acetic acid. The twelfth example of this paper size is applicable to China National Standard (CNS) A4 (21〇X 297 public love) 66 II ---; | 7 ---------- " —Order h --- ----- Line · (Please read the notes on the back before filling this page)

5. Description of the invention (64) In an aqueous solution (45 ml) of sodium tetrakisdium palladium (1.90 g) and tetrakisauric acid tetrahydrate (05 () g), a silicon oxide carrier [KA-1, Particle size: 5 mm p, product of Zud-chemie AG] (69 g) to absorb the lining of the king. Then, it was added to an aqueous solution (100 ml) of sodium metapetite octahydrate (6.9 g), and the mixture was allowed to stand at room temperature for 20 hours. Then, hydrazine monohydrate (6.5 g) was added and stirred slightly, and the mixture was allowed to stand at room temperature for 4 hours to reduce to metal palladium. After filtering the catalyst and performing decantation, 'transfer it to a glass column equipped with a cock' and pass purified water for 40 hours at a rate of 1.5 liters of mother hour 'for cleaning . It was then dried for 4 hours under an air current of 110 to obtain a metal-filled catalyst. The catalyst filled with metal palladium was then added to an aqueous solution (45 ml) of sodium alumite (0.12 g) to absorb the entire amount. Then at 110. (: Dry under an air stream for 4 hours to prepare a π-th catalyst for the production of acetic acid. In addition to replacing the tetrakisauric acid of the twelfth example with zinc chloride (0.08 g), The same method was used to prepare the thirteenth catalyst for the production of acetic acid. The fourteenth example was the same as the twelfth example except that the tetrakisauric acid of the twelfth example was replaced with chromium chloride hexahydrate (0.22 g) Method to prepare the 14th catalyst for the production of acetic acid. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------- installation ---- ---- Order --------- line (Please read the notes on the back before filling out this page) Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 67 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 1835 A7 ----___ B7 ____ V. Description of Invention (65) The first comparative example

In an aqueous solution (45 ml) of sodium tetrapalladate (1.90 g) and an aqueous solution (45 ml), a silica carrier [KA-1, particle size: 5 mm p, product of Zud_chemie AG] (69 g) was added to absorb all of the the amount. This was then added to an aqueous solution (100 liters) of sodium metasilicate nonahydrate (5.5 g), and the mixture was allowed to stand at room temperature for 20 hours. Then hydrazine monohydrate (5 g) was added and gently stirred, and the mixture was allowed to stand at room temperature for 4 hours to reduce to metal palladium. After the catalyst was filtered and decanted, it was transferred to a glass column equipped with a cock, and purified water was passed at a rate of 5 liters per hour for 40 hours for cleaning. Then, it was dried for 4 hours under a gas of 1 j OC> 'IL to obtain the first $ 1 catalyst for the production of acetic acid. JL's vowel analysis of catalysts for the production of acetic acid will use (a) palladium, a (b) group of elements and / or a (c) group of catalysts for the production of acetic acid, using aqua regia and / or hydrofluoric acid and The aqua regia mixture is heat-treated to completely extract the constituents, and measured by inductively coupled proton (ICP) release spectroscopy. The (JCP) release spectrometer used was SPS-1700 manufactured by Seiko Denshi Kogyo, KK. The weight ratios of the respective components of the 1st to 5th catalysts prepared in the first to fourth examples and the first comparative example, and the mole ratios of the respective components to palladium are shown in Table 1. The percentage values in the table represent weight percentages relative to each catalyst. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) 68; --- :: called --- · Ί-^^^ ------ 卜 —Order "--- ----- Xiong Lu (please read the precautions on the back before filling this page) 491835 A7 B7 V. Description of the invention (66) Table 1 Catalyst No. printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs Catalyst composition (a ) Catalyst composition (b) Catalyst composition (C) Palladium of the first catalyst 0.86% Pound 0.091% (# / Palladium = 0.09) Palladium of the second catalyst 0.86% Palladium 0.54% (4K / palladium = 0.33) Palladium of the third catalyst 0.86% recorded 0.091% (i / palladium = 0.09) Palladium 4th catalyst 0.86% Palladium 0.198% (Bismuth / Palladium = 0.12) Palladium 5th catalyst 0.86% Tin 0.180% (Sn / Pd = 0.19) Palladium 6th catalyst 1.11 % m 0.H7% (pound / palladium = 0.09) Palladium 7 catalyst 0.59% Pound 0.062% (Pound / palladium = 0.09) Palladium 8 catalyst 0.86% Gold 0.30% (Gold / Palladium = 0.19) Palladium 9 catalyst 0.86 % Zinc 0.10% (zinc / palladium = 0.10) 10th catalyst palladium 0.86% chromium 0.07% (chromium / palladium = 0.14) 11th catalyst palladium 0.86% manganese 0.088% (manganese / palladium = 0.20) 12th catalyst palladium 0.86% # 0.091% (谛 /palladium=0.09) gold 0.30% (gold / palladium = 0.19) 13th catalyst palladium 0.86% pound 0.091% (record / palladium = 0.09) zinc 0.10% (zinc / palladium = 0.10) 14th catalyst palladium 0.86% pound 0.091% (record / palladium = 0.09 ) Chromium 0.09% (Cr / Pd = 0.15) 15th catalyst palladium 0.86% 15th to 28th examples and 2nd comparative example [manufactured by acetic acid] SUS316 reaction tube (inner diameter 25mm) was filled in the 1st to 14th examples Compared with 12.5 ml of the catalyst used in the first comparative example to produce acetic acid, the reaction is based on a catalyst bed with a reaction peak temperature of 160 ° C and a reaction pressure of 0.8 MPa. (This paper applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -69-— — — — — — — — — — II (Please read the notes on the back before filling this page) ΙΊ · --- line 491835 A7 B7_ V. Description of the invention (67 ) Under the instrument pressure), a supply gas is introduced, which includes a mixture of ethanol, oxygen, steam and nitrogen with a volume ratio of 2.5 ·· 6: 25 ·· 66.5, and a volume rate of 4400 hours4. The generated gas was cooled, and the collected condensed reaction solution was analyzed by gas chromatography (GC-14B, Shimazu Kagaku, KK. FID). The activity of each catalyst is calculated based on the gram of acetic acid (space-time yield, STY) produced per liter of catalyst per hour, and the selectivity is calculated based on the product percentage relative to the starting ethanol. The reaction results are shown in Table 2. (Please read the precautions on the back before filling this page) Example number printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Catalyst composition STY grams of acetate per hour liter of catalyst ethanol conversion rate ° / acetic acid selectivity% ethyl acetate% B Aldehyde% Carbon dioxide% Fifteenth case 1 Pound 193 79 83 12 0.7 2.2 Sixteenth case 2 186 70 90 11 1.0 1.8 Seventeenth case 3 In Pakistan-Record 198 80 84 11 1.0 1.8 Eighteenth case 4 184 80 78 12 2.3 5.6 19th case 5 Daba · Tin 163 73 76 12 2.3 8.6 20th case 6 Emperor 203 82 84 11 0.8 3.0 21st case 7 Daba-Record 138 72 65 20 2.0 8.0 22nd case 8 Palladium-Gold 183 83 75 14 2.0 8.2 23rd case 9 Palladium-zinc 159 75 72 13 2.3 12.1 24th case 10 Palladium-chromium 142 72 70 12 2.4 14.3 25th case 11 Palladium-hard 168 80 74 12 0.4 10.3 26th case 12 Emperor-Gold 220 88 85 5 1.0 3.0 27th case 13 Mingba-Lu-Ci 244 90 92 3 1.4 3.1 28th Case 14 Ji-Lu-Luo 226 89 90 4 1.2 4.1 2nd Comparative Example 15 Palladium itself 120 54 63 7 4.5 25.0 70 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 491835 A7 B7 Warp Printed by the Employees ’Cooperative of the Ministry of Intellectual Property Bureau. 5. Description of the invention (68) The 29th example was added with a silicon oxide carrier in an aqueous solution (45 ml) of sodium tetrakistridium [Na2PdCl4, product of Takana Kikinzoku] (1.90 g). [KA-1 'Particle size: 5¾ mp, product of Zud-chemie AG] (69 g)' to absorb the entire amount. Then, it was added to an aqueous solution (100 ml) of sodium metasilicate nonahydrate [Na2Si03 · 9H20, product of Wako Junyaku] (3.8 g), and the mixture was allowed to stand at room temperature for 20 hours. Then, hydrazine monohydrate [N2Η4 · H20] (5 g) was added and stirred slightly, and the mixture was allowed to stand at room temperature for 4 hours to reduce to metal palladium. After the catalyst was filtered and decanted, it was transferred to a glass column equipped with a cock, and purified water was passed for 40 hours for cleaning. Then, it was dried for 4 hours under a gas flow of 10 ° C to prepare a catalyst filled with metal ε. The catalyst filled with metal palladium was then immersed in an aqueous solution (45 ml) of tungsten silicic acid η hydrate [H4SiW12〇4〇 * ηΗ20 »η = 20-30» Product of Nihon Muki Kagaku Kogyo] (44 g) . This addition was done once, and the mixture was gently stirred by rotation until the solution was completely absorbed (about 3 minutes). After impregnation, the wet impregnated support was allowed to stand at room temperature for 1 hour. In the oven. After drying under a stream of 0 for 4 hours, it was allowed to stand in a desiccator overnight. Thus, a first catalyst for producing acetic acid and ethyl acetate was prepared. Example 30 Except for tungsten phosphate n-hydrate [H3PW1204. · ΗΗ20, η = 20-30 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public copy) 71 ------------- Installation -------- 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 491835 A7 B7 V. Invention Description (69), Nihon Muki Kagaku Kogyo Company The product] (59 g) was used instead of the tungsten silicic acid η hydrate of Example 29, and a second catalyst for producing acetic acid and ethyl acetate was prepared by the same method as in Example 29. In the 31st example, an aqueous solution (45 ml) of manganese tungsten silicate was used instead of the η-hydrate of tungstosilicic acid in the 29th example, and the same method as in the 29th example was used to prepare acetic acid and ethyl acetate. Third catalyst. An aqueous solution of manganese tungsten silicate is prepared by dissolving manganese nitrate hexahydrate [Μη (Ν03) 2 · 6H20, a product of Wako Junyaku Co., Ltd.] (0.38 g) in tungsten tungstic acid η hydrate (44 G) in water. In the 32nd example, an aqueous solution (45 ml) of copper tungsten silicate was used instead of the eta-tungstate hydrate of the 29th example, and the same method as in the 29th example was used to prepare acetic acid and ethyl acetate. Fourth catalyst. An aqueous solution of copper tungsten silicate is prepared by dissolving copper nitrate trihydrate [Cu (N03) 2 · 3H20, a product of Wako Junyaku] (0.32 g) in a tungsten silicic acid η hydrate (44 g). In aqueous solution. Thirty-three cases were added to an aqueous solution (56 ml) of sodium tetrachloroethylene (1.90 g), and a silicon oxide carrier [〇 八 1 ^ 八 (: 丁, (^ 10,? 18111 (^ & Chemistry) Company's product] (55 g) to absorb the entire amount. Then it was added to an aqueous solution (100 ml) of sodium metasilicate nonahydrate (4.0 g), and the mixture was allowed to stand at room temperature for 20 hours. Then add hydrazine monohydrate (5g) and stir it slightly, so that the size of the mixed paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -72--; ---- 1 ^. --- Λ —------- r— -------- line (please read the precautions on the back before filling this page) 491835 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _______B7__ 5 7. Description of the invention (70): The mixture is allowed to stand at room temperature for 4 hours to reduce to metal palladium. After the catalyst is filtered and decanted, it is transferred to a glass column equipped with a cock, Purified water was passed in for 40 hours for washing. Then, it was dried under an air flow at 110 ° C for 4 hours to obtain a filling product. Metal catalyst. The catalyst filled with metal palladium is then impregnated with tungsten phosphoric acid ^ hydrate

A

[H3PW12〇4〇 · ηΗ20 »η = 20-30» Product of Nihon Muki Kagaku Kogyo] (45 g) in an aqueous solution (56 liters). The addition was performed once and the mixture was gently stirred by rotation until the solution was completely absorbed (about 3 minutes). After impregnation, the wet impregnated support was allowed to stand at room temperature for 1 hour. After drying for 4 hours under an air flow in an oven, it was allowed to stand in a desiccator overnight. Thus, a fifth catalyst for producing acetic acid and ethyl acetate was prepared. In the 34th example, a silicon oxide carrier [KA-1, particle size: 5 mm φ, zud-chemie AG was added to an aqueous solution (45 ml) of sodium tetrachloropalladate [Na2PdCl4, product of Takana Kikinzoku] (1.90 g). Company's products] (69 g) to absorb the entire amount. It was then added to an aqueous solution (100 ¾ liters) of sodium metasilicate nonahydrate [N_〇3 · 9Η20, a product of Wak0 Junyaku] (38 g), and the mixture was allowed to stand at room temperature for 20 hours. . Then, hydrazine monohydrate [N2Η4 · Η20] (5 g) was added and stirred slightly, and the mixture was allowed to stand at room temperature for 4 hours to be reduced to a metal bar. After the catalyst was decanted and decanted, it was transferred to a paper equipped with a spinner. The paper was compliant with China National Standard (CNS) A4 (21 × X 297). -73 ^ ------ -^ —------- ^ (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 A7 -------------- --- V. Description of the invention (? 1) Stoppered glass tube column, and pass purified water for 40 hours for cleaning. Then, it was dried under an air flow of 110 ° C for 4 hours to prepare a catalyst filled with a metal handle. The catalyst filled with metal palladium was then impregnated with tungsten silicic acid ^ hydrate [H4SiW12O40. ΗΗ20 »η = 20-30» Nihon Muki Kagaku Kogyo's product] (44 g) and osmic acid [H6Te〇6, Kanto Kagaku Company's product] (0.13 g) in aqueous solution (45 ml). This addition was done in one time 'and the mixture was slightly stirred by rotation until the solution was completely absorbed (about 3 minutes). After impregnation, the wet impregnated support was allowed to stand at room temperature for 1 hour. After drying for 4 hours under an air current of 0 cc in an oven ', it was allowed to stand in a desiccator overnight. Thereby, a sixth catalyst for producing acetic acid and ethyl acetate was prepared. The 35th example was replaced by the bismuth nitrate pentahydrate [Bi (N03) 2 · 5H20, a product of Wako Junyakii] (0.40 g) in the 35th example by the same as in the 34th example By the method, a seventh catalyst for producing acetic acid and ethyl acetate was prepared. In the 36th example, a silicon oxide carrier was added to an aqueous solution (45 ml) of sodium tetrapalladate sodium (1.90 g) and tetragas auric acid tetrahydrate [h4AuC14 • 4H20, product of Takana Kikinzoku] (0.50 g). [KA- 丨, particle size: 5 mmP, product of Zud-chemie AG] (69 g) to absorb the entire amount. It was then added to an aqueous solution of sodium metasilicate nonahydrate (5.2 g) (100 paper sizes applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 74-^ ---- ^ 1- --Λ --------- ------------ ^ ---- V-* (Please read the notes on the back before filling out this page) Intellectual Property of the Ministry of Economic Affairs A7 printed by the Bureau's Consumer Cooperatives -------- B7___ 5. In the description of the invention (72)-pen liter), let the mixture stand at room temperature for 20 hours. Then add hydrazine • monohydrate (6.5 g) and gently stir, and let the mixture stand at room temperature for 4 hours 4 ′ to reduce to metal age. After the catalyst was filtered and decanted, it was transferred to a glass column equipped with a cock, and purified water was passed in for 40 hours for washing. Then, it was dried for 4 hours under the air flow of U (rc) to obtain a catalyst filled with metal palladium. Then the catalyst filled with metal age was impregnated with tungsten silicic acid 11 hydrate [H4SiW12O40. NH20 ^ n = 20- 30, Nihon Muki Kagaku Kogyo's product] (44 g) in an aqueous solution (45 ml). This addition is done once and the mixture is gently stirred by rotation until the solution is completely absorbed (about 3 minutes) ). After impregnation, let the wet impregnated carrier stand at room temperature for 丨 hours. Dry the olefin under the air flow of 丨 丨 in the oven for 4 hours, then let it stand still in the desiccator. It was left overnight. Thus, an eighth catalyst for producing acetic acid and ethyl acetate was prepared. In addition to the 37th example, zinc chloride [ZnCl2, a product of Wako Junyaku Co., Ltd.] (0.08 g) was used instead of the fourth example. The ninth catalyst for the production of acetic acid and ethyl acetate was prepared by the same method as in the 36th example except for the gas auric acid tetrahydrate. &Quot; The 38th example Weng • The acid in Siqi Sodium (3.80 g) and zinc chloride (0.14 g) in an aqueous solution (45 ml) Add silicon oxide carrier [ΚΑ-1, particle size: 5 mm ρ Zud-chemie AG's product] (69 g) to absorb the entire amount. This paper size applies Chinese National Standard (CNS) A4 (21G X 297)公 ίΐ " Factory 75 _ — 1 — — — — — — — — — — — 1111111 a — — — — — — (Please read the notes on the back before filling out this page)

After printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, it was added to an aqueous solution (1 milliliters) of sodium metapetite octahydrate (81 g), and the mixture was allowed to stand at room temperature for 20 hours. Then hydrazine monohydrate (6.5 g) was added and gently stirred, and the mixture was allowed to stand at room temperature for 4 hours to reduce to metal palladium. After the catalyst was filtered and decanted, it was transferred to a glass column equipped with a cock, and purified water was passed through 40% by weight. Then at i 1〇. 〇Drying for 4 hours under an air stream to prepare a zinc-containing catalyst filled with metal palladium. 〇Then the catalyst filled with metal palladium was immersed in an aqueous solution (45 g) of sodium poundite (0.27 g) To absorb the entire amount. Then, it was dried under a stream of sn (rc) for 4 hours to prepare a metal-palladium-filled catalyst containing pounds and zinc. Then, the catalyst filled with metal was impregnated with tungsten oxalate n hydrate [H4SiW12O40 · nH20, n = 20-30, Nihon Muki Kagaku Kogyo's product] (24 g) in an aqueous solution (45 ml). This addition is done once and the mixture is slightly stirred by rotation until the solution is completely absorbed by 70 (About 3 minutes). After the impregnation effect, let the wet impregnated carrier stand at room temperature for 1 hour. Dry it for 4 hours under the air current of i 〇c in the oven and let it It was left to stand in a desiccator overnight. Thereby, a 10th catalyst for producing acetic acid and ethyl acetate was prepared. The 39th example was tetrasodium hexahydrate (2.76 g) and tetrachloroauric acid tetrahydrate (0.78). G) in an aqueous solution (45 ml), with the addition of a silicon oxide carrier [ΚΑ-1, the particle size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) i — -------- --ί -------- line · (Please read the precautions on the back before filling in this page) 76 491835 A7 _______B7__ printed by the Consumers' Cooperative of the Ministry of Economics and Intellectual Property of the Ministry of Economic Affairs of the People's Republic of China. V. Invention Description (74): 5mm p, product of Zud-chemie AG] (69 g) to absorb the entire amount. Then it Add to an aqueous solution (100 ml) of sodium metasilicate nonahydrate (83 g), and let the mixture stand at room temperature for 20 hours. Then add hydrazine monohydrate (6.5 g) and gently stir to allow The mixture was allowed to stand at room temperature for 4 hours to reduce to metal palladium. After the catalyst was filtered and decanted, it was' transferred to a glass column equipped with a cock and passed through purified water 40 Hours for cleaning. Then dried under a current of 110 ° C for 4 hours to prepare a gold-filled metal-filled catalyst. The iron-containing catalyst was then impregnated in iron stone. Acid η hydrate [H4SiW1204〇 · ηΗ20, η = 20-30, Nihon Muki

Kagaku Kogyo's product] (24 g) and sodium pound (0 28 g) in a water solution (45 ml) to absorb the entire amount. Then, it was dried for 4 hours under a stream of 1100C to obtain a metal-palladium-filled catalyst containing pounds and zinc. ; ,,; The catalyst loaded with metal palladium was then impregnated with tungsten silicic acid n hydrate [H4SiW1204. ΗΗ20, η = 20-30, a product of Nihon Muki Kagaku Kogyo] (24 g) in an aqueous solution (45 ml). The addition was artificial-and the mixture was slowly stirred by rotation until the solution was absorbed by the king (about 3 minutes). After impregnation, the immersed dipped carrier was allowed to stand at room temperature for 1 hour. After drying for 4 hours under an air flow of 1 100 ° C in an oven, it was allowed to stand in a desiccator overnight. Thus, a first catalyst for producing acetic acid and ethyl acetate was prepared. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------------- Packing ----------- Order -------- -Line (please read the precautions on the back before filling this page) 77 491835 Printed clothing A7 B7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (75) The 40th example will be cyanic acid η hydrate [H3PW12〇 4. ΗΗ20, η = 20-30, a product of Nihon Miiki Kagaku Kogyo] (150 g) dissolved in water (75 ml) to prepare an aqueous solution of tungstic acid. Under an aqueous solution of violently dropping tungsten phosphonic acid, cesium nitrate [CsN03, a product of Wako Junyaku] (25 g) was added dropwise using a dropping funnel over a period of 5 minutes to obtain a slurry of tungsten cesium phosphate. precipitation. While vigorously stirring the slurry-like precipitate, using a dropping funnel, dropwise add acetic acid [P (i (〇Ac) 2] (i 1.7 g)) in acetone (10 liters) over a period of 5 minutes, and then The mixture was stirred for 1 hour. The solvent was then removed on a rotary evaporator, the precipitate was removed, and the precipitate was dried under an air flow at 1 500C for 3 hours. The produced palladium-containing tungsten phosphate shaved salt Grind to a particle size of 3-5 mm, dry under a 200 ° C air flow for 3 hours, and perform a reduction treatment with a 250 ° C hydrogen flow for 5 hours to obtain a first 12 catalyst. Comparative Example 3 In an aqueous solution (45 ml) of sodium tetrakis-sodium (1.90 g), a stone oxide carrier [KA-1, particle size: 5 mm φ, product of Zud_chemie AG] (69 G) to absorb the entire amount. It was then added to an aqueous solution (100 ml) of sodium metasilicate nonahydrate (5.5 g) and the mixture was allowed to stand at room temperature for 20 hours. Then hydrazine was added Monohydrate (5 g) and slightly stirred, let the mixture stand at room temperature for 4 hours To reduce to metal palladium. After filtering the catalyst and decanting, it is transferred to a glass column equipped with a cock and passed through purified water for 40 hours. This paper applies Chinese national standards. (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling out this page)-* 1 · ϋ n ϋ 1 · 1 «^ 1 ϋ ϋ ϋ I n HI ^ 78 Printed by the Property Agency Staff Consumer Cooperative

Description of the invention (76) 'for cleaning action. It was then dried under a stream of 110 ° C for 4 hours to prepare a 13th catalyst for producing acetic acid and ethyl acetate. Comparative Example 4: A 7-alumina support [NST-3, particle size: 3.2 mm p, product of Nikki Universal] was added to an aqueous solution (30 ml) of sodium tetrachloropalladate (1.90 g). (50 g ) To absorb the full amount. It was then added to an aqueous solution (100 ml) of sodium metasilicate nonahydrate (5.5 g), and the mixture was allowed to stand at room temperature for 20 hours. Then hydrazine monohydrate (5 g) was added and gently stirred, and the mixture was allowed to stand at room temperature for 4 hours to reduce to metal palladium. After the catalyst was filtered and decanted, it was transferred to a glass column equipped with a cock, and purified water was passed for 40 hours' for cleaning. It was then dried under a stream of 1 HTC for 4 hours to prepare a 14th catalyst for the production of acetic acid and ethyl acetate. Elemental analysis of catalysts intended to produce acetic acid and ethyl acetate will contain (a) metal palladium, (b) inorganic acids and / or salts thereof and / or one (c) group of elements and / or one (d) group The catalyst of the element is heat-treated with aqua regia and / or a mixture of hydrofluoric acid and aqua regia to completely extract each component, and measured by inductively coupled plasma (ICP) emission spectroscopy. The (ICP) release spectrometer used is the SPS-1700 manufactured by Seiko Denshi Kogyo, KK. The 29th to 40th examples and the 3rd to 4th comparison examples of the respective components of the catalysts prepared in the 1st to 14th catalysts The weight ratio is shown in Table 3. The percentage values in the table represent weight percentages relative to each catalyst. The weight of the heteropoly acid is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 public love) — — — — — — — — — — 1 · · II 丨 I 丨 II, 1 ^ · 1111111 · ( (Please read the notes on the back before filling this page) 79 491835 A7 _ B7___ V. Description of the invention (77) The percentage of the amount is expressed by the value calculated for the molar weight of each corresponding anhydride. For the elements of group (c) and group (d) in Table 3, the mole ratio of each element to the element is shown in parentheses. Table 3. Catalyst No. printed by the employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Catalyst composition (a) Catalyst composition (b) Catalyst composition (c) Catalyst composition ⑹ The first catalyst palladium 0.58% tungsten silicic acid (H ^ iWuCy 32.2%--Palladium 2nd catalyst-% Tungstophosphoric acid (H3PW12〇4〇) 33.8%--Palladium 3rd catalyst 0.58% Manganese salt of tungsten silicic acid (Mn01H36SiW12O40) 33.0% Palladium 4th catalyst 0.60% Copper of tungsten silicic acid Salt (CUdHuSiWuOJ 34.3% 5th catalyst palladium 0.63% tungsten silicic acid (H4SiW12〇4〇) 42.2%--6th catalyst palladium 0.57% tungsten silicic acid (H4SiW12〇4〇) 33.0% pound 0.11% (_bar = 0.09) -7th catalyst palladium 0.57% tungsten silicic acid (H4SiW12〇4〇) 33.3% bismuth 0.23% (heterobar = 0.12)-8th catalyst palladium 0.57% tungsten silicic acid (H4SiW12〇4〇) 32.1%-gold 0.20% ( Gold / palladium = 0.09) Palladium 0.57% Tungsten Silicic Acid (H4SiW12〇4〇) 31.8%-Zinc 0.03% (Zinc / Palladium = 0.10) Palladium 10th Catalyst 1.46% Tungsten Silicic Acid (H4SiW12〇4〇) 22.4 % 0 0.062% (Record / palladium = 0.09) Zinc 0.10〇 / 〇 (Zinc / Palladium = 0.10) 11th catalyst palladium 1.06% Tungsten silicic acid (H4SiW12〇4〇) 24.4% # 0.063% ( /Palladium=0.11) gold 0.40% (gold / palladium = 0.19) palladium of the 12th catalyst 3.6% cesium salt of tungsten phosphoric acid (Cs ^^ Ao) 96.0% palladium of the 13th catalyst 0.58%---palladium of the 14th catalyst 1.10% • --(Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 80 491835 A7 B7 V. Description of Invention (78) 41-52 cases Comparative Examples 5 and 6 [Manufacture of Acetic Acid and Ethyl Acetate] The SUS3 16 reaction tube (inner diameter 25 mm) was filled in the 29-40th example and the 3rd and 4th comparative examples to — 25.0 ml of catalyst for the production of acetic acid and ethyl acetate, the reaction is performed at a catalyst bed reaction peak temperature of 160 ° C and a reaction pressure of 0-8 MPa (meter pressure). A supply gas is introduced, which includes a volume ratio of 10: 6: 25: 59, a mixture of ethanol, oxygen, steam and nitrogen, and a volume velocity of 1800 hours μ. The generated gas was cooled, and the collected condensed reaction solution was analyzed by gas chromatography (GC-14B, Shimazu Kagaku, KK · FID). The activity of each catalyst is calculated based on the gram of acetic acid (space-time yield, STY) produced per liter of catalyst per hour, and the selectivity is calculated based on the product percentage relative to the starting ethanol. The reaction results are shown in Table 4. a (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 81-491835 A7 B7 V. Description of the invention (79) Table 4 Example No. Catalyst STY (g / h liter catalyst) Conversion rate (%) 1%) Ethyl acetate Ethyl acetate Ethyl acetate Carbon dioxide Acetaldehyde Diethyl myth Ethylene Example 41 1 172 45 63 78 15 2.3 3.3 1.7 0.2 42 2 177 50 65 77 16 3.5 2.1 1.0 0.2 43 3 170 53 65 74 17 3.0 3.2 2.0 0.2 44 4 170 16 60 80 11 2.9 3.2 2.0 0.2 45 5 182 38 66 78 12 3.3 3.5 1.5 0.5 46 6 121 25 51 67 10 0.7 4.4 13.0 1.8 47 7 124 29 50 70 12 1.0 3.1 13.0 1.0 48 8 193 47 70 78 14 2.0 1.3 1.6 1.5 49 9 212 43 75 80 12 2.3 2.8 1.5 0.5 50 10 177 121 81 62 31 1.3 0.4 1.1 4.2 51 11 189 119 85 63 28 1.2 0.4 1.0 3.8 52 12 69 66 40 49 34 5.3 5.3 2.3 3.3 Comparative example 5 13 30 108 49 21 56 15 8.0 0.0 0.3 6 14 42 32 30 40 22 20 10.2 6.0 2.3 (Please read first Please fill in this page again.) 53-56 cases printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [manufacturing of acetic acid and ethyl acetate] Filled in the 38th case in a SUS3 16 reaction tube (inner diameter 25 mm) The prepared 10th catalyst (25.0 ml) for producing acetic acid and ethyl acetate was reacted at a catalyst bed reaction peak temperature of 160 ° C and a reaction pressure of 0.8 MPa (instrument pressure). A supply gas was introduced. It includes a mixture of ethanol, oxygen, steam, and nitrogen with a volume ratio (%) of X: 6 ... 25: (69-X), and a volume rate of 1800 hours. " The ethanol gas concentration (X%) is shown in Table 5. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 82 Description of the invention (80) The generated gas is cooled and then analyzed by gas phase chromatography ... ^ 14B, Shimazu Kagaku, KK. (FID) analysis of the collected condensed reaction solution. The activity of each catalyst is calculated in grams of acetic acid (space-time yield, STY) produced per liter of catalyst per hour, and selectivity is calculated in terms of the percentage of the product relative to the starting ethanol. The reaction results are shown in Table 5. Table 5 Example No. Ethanol Gas Concentration (%) STY (g, liters / hour public reagent) Conversion Rate (%) Selectivity (%) Ethyl Acetate Ethyl Acetate Ethyl Acetate Carbon Diacetate Acetaldehyde Diethyl Ethylene 53 2.5 5 104 98 6 92 2.2 0.1 0.0 0.0 54 54 46 175 93 26 72 2.0 0.3 0.3 0.0 55 10 157 120 81 62 31 1.3 0.4 1.1 4.2 56 15 279 75 70 72 14 0.6 0.4 5.5 7.2 As explained above, borrow By using a catalyst for the production of acetic acid, it comprises (b) at least one element selected from the group consisting of (b) at least one element selected from the group consisting of: Or (c) at least one element selected from the group of elements of Groups 6, 7, 8, 9, 10, 11 and 12 of the periodic table to prepare a catalyst for producing acetic acid from ethanol and oxygen, and Acetic acid can be produced with a higher space-time yield, lower selectivity of carbon dioxide and acetaldehyde, and the lowest degradation effect compared to catalysts of conventional technology, and thus higher production efficiency. A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (81) Going further 'by using a catalyst for the production of acetic acid and ethyl acetate.%, Which contains a metal catalyst added ( b) at least one compound selected from the group consisting of inorganic acids and their salts and / or at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table and / or (d) at least one An element selected from the group consisting of elements of groups 6, 7, 8, 9, 10, 11, and 12 of the periodic table to prepare a catalyst for producing acetic acid and ethyl acetate from ethanol and oxygen, and Compared with conventional catalysts, it has higher emptying yield, lower selectivity and minimum degradation of dioxin and ethyl, and therefore higher production efficiency. . Clothing k ^ -------------------------------- • Qiao--11 .. (Please read the precautions on the back first (Fill in this page again) _ (CN quasi-standard home country, middle school, moderate j rule, one piece of paper, one secret 97 84

Claims (1)

491835 ^ Shadow II P A8 B8 C8 D8 ir / J Patent Application No. 089106562 Patent Application Patent Application Amendment Date of Amendment: January 91 1. A catalyst for the production of acetic acid by the reaction of ethanol and oxygen, which includes a fixed on (A) Palladium and (b) at least one element selected from the group consisting of elements of Groups 14, 15 and 16 of the Periodic Table on a carrier. 2. A catalyst for the production of acetic acid by the reaction of ethanol and oxygen, comprising (a) and (c) at least one element selected from the group consisting of: Elements of groups 7, 8, 9, 10, 11 and 12. 3. A catalyst for the production of acetic acid by the reaction of ethanol and oxygen, comprising (a) palladium, (b) at least one element selected from the group consisting of: Elements of groups 15 and 16 and (c) at least one element selected from the group consisting of elements of groups 6, 7, 8, 9, 10, 11, and 12 of the periodic table. 4. The catalyst according to any one of claims 1 to 3, wherein the (a) handle is a metal handle. 5. The catalyst according to any one of claims 1-3, wherein the support is silicon oxide. 6. The catalyst according to item 丨 or 3 of the scope of patent application, wherein the at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table is selected from the group consisting of code, pound, antimony, silver, tin and ferry. 7. The catalyst according to item 2 or 3 of the scope of patent application, wherein (c) at least one element selected from the following group: Periodic Table 6, 7, 8, 9, 9. ) ^ 格 ⑵0X297 公 爱) — ί ---------------- ----- d Order ----- U ——, ··· Please read the first Note for this page, please fill out this page) 〇JO 上 〇JO A8B8C8D8 The elements of groups W, 11 and 12 are selected from chromium, gold, manganese and zinc. 8. A method for manufacturing a catalyst for producing acetic acid as described in the scope of the patent application, including the following first and second steps: The first step is a step in which (a) metal palladium is loaded on a carrier In order to obtain a catalyst filled with metallic palladium; the second step is a step in which (b) at least one element selected from the group consisting of halogens, groups 14, 15 and 16 of the periodic table is charged at the first! Step The obtained catalyst was filled with a metal, to obtain a catalyst for producing acetic acid. 9. A method for manufacturing a catalyst for the production of acetic acid, as in item 3 of the scope of patent application, comprising the following first and second steps: The first step is a step in which (a) a palladium compound, (b) at least An element selected from the group "Elements of Groups 14, 15 and 16 of the Periodic Table and (C) at least one element from the Groups of Groups ... Groups 6, 7, 9, 10, 11 and 12 of the Periodic Table Elements are loaded on a carrier to prepare a catalyst filled with a kimono compound; the second step is a step in which the catalyst filled with a kimono compound obtained in the first step is reduced to produce a seed Catalyst for the production of acetic acid. H) .- A kind of catalysis for the production of acetic acid, such as the scope of the patent application No. 3 This paper applies the Chinese National Standard (CNS) M standard (21〇297297) 86 491835. A method for manufacturing a patent-applied agent, which includes the following step (i): The first step is where at least one of the compound E and plutonium is selected from the following groups: Periodic Table 6, 7, 8, 9, 10, n and thorium elements are loaded on __, "to obtain _ kinds of catalysts containing palladium compounds; 'The second step into the first step', wherein the prepared in the first step is filled with a chemical One catalyst is reduced to obtain a kind of catalyst loaded with metal; the third step is a step in which (b) at least one element selected from the group consisting of elements of groups 15 and 16 of the periodic table is charged in The catalyst prepared in the second step is packed with a metal catalyst to produce a catalyst for producing acetic acid. 11.-A method for producing acetic acid ', which is included in items 1 to 7 as in the scope of patent application Ethanol is reacted with oxygen in the presence of a catalyst for the production of any one of acetic acid. 12. The method according to item 丨 丨 of the patent application, wherein ethanol reacts with oxygen in the presence of water. 13. If applied Patent scope 丨 丨 or ^ In which ethanol and oxygen are reacted in a liquid phase. 14. The method of item 11 or 12 in which the scope of the patent application is applied, in which ethanol and oxygen are reacted in a gas phase. The paper size is suitable for China National Standard (CNS) A4 Specifications U10X297 mm) IIIIIIIIIIII IV.— IJ (please read the notes on the back before filling in this page) f · .t, 491835 < 1 Α8 Β8 C8 D8 Application scope of patent 15 · If the method of the scope of patent application No. 14 is used, water The concentration in the starting gas is 0.1 to 50% by volume. 16. The method according to claim 11 in which the starting gas or liquid system is blended with acetaldehyde and / or diethyl ether and then reacted. 17. · A catalyst for the production of acetic acid and ethyl acetate by the reaction of ethanol and oxygen, comprising (a) le and (b) at least one compound selected from the group consisting of inorganic acids and their salts . 18. · A catalyst for the production of acetic acid and acetic acid acetate by the reaction of ethanol and oxygen, including (a) and (b) at least one compound selected from the group consisting of inorganic acids and their salts and (C) At least one element selected from the group consisting of elements of Groups 14, 15 and 16 of the Periodic Table. 19. A catalyst for the production of acetic acid and ethyl acetate by the reaction of ethanol and oxygen, comprising (a) palladium, (b) at least one compound selected from the group consisting of: inorganic acids and their salts and (At least one element selected from the following group ... An element of Groups 6, 7, 8, 9, 10, and imi2 of the periodic table. 20 · —A kind of acetic acid and ethyl acetate produced by the reaction of ethanol and oxygen A catalyst for vinegar, comprising 0) palladium, (b) at least one compound selected from the group consisting of: inorganic acids and their salts, and (c) at least one element selected from the group consisting of: 14, 15 and Elements of group 16 and (d) at least one element selected from the group consisting of elements of groups 6, 7, 8, 9, 10, 11 and 12 of the periodic table. 21. The catalyst as claimed in any one of claims 17 to 20, wherein (a) is a metal handle. This paper size applies the Chinese National Standard (CNS) M specification (21〇 < 297mm) ------------------------ Packing .. ...... Order .................. line · (Please read the precautions on the back before filling in this page ) -88 491835 A8 B8 C8 ______D8 VI. Application for patent scope 22. For the catalyst according to any one of the patent applications No. ι7 to 20, in which (b) at least one compound selected from the group of inorganic acids and The salts thereof are selected from the group consisting of phosphoric acid and its salts and heteropolyacids and their salts. 23. The catalyst according to any one of claims 7 to 20, wherein (b) at least one is selected from the following Compounds in the group: inorganic acids and their salts are selected from the group consisting of heteropoly acids and their salts, and the heteropoly acids are selected from the group consisting of silicotungstic acid, phosphotungstic acid, silomolybdic acid, phosphomolybdic acid, silicovanadium Acid, phosphatidronic acid, crushed jelly acid and squamous acid. 24. The catalyst as claimed in claim 18 or 20, wherein (c) at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table is selected from selenium, pound, antimony, bismuth and lead. 25. A catalyst as claimed in item 19 or 20 of the scope of patent application, wherein the (sentence at least one element selected from the following group ... the elements of the periodic table 6, 7, 8, 9 10 11 and 12 are not selected from 26. For example, the catalyst of any one of items 17 to 20 of the scope of patent application, wherein the catalyst's constituents are fixed on a carrier. 27. If the scope of application for specialty 26 The catalyst according to item 1, wherein the carrier is oxidized stone. 28. A method for producing a catalyst for producing acetic acid and ethyl acetate according to item 17 of the scope of patent application, which includes the following first and second steps: 1 step is a step in which (a) metal is loaded on a carrier, (CNS) A4 ^ (210 X 297 ^ *) '~ " (Please read the precautions on the back before filling this page); order ▼ line 丨 ~, apply for a patent to obtain a catalyst filled with metal palladium; Step 2 is a step in which (b) at least one compound selected from the group consisting of inorganic acids and their salts is charged On a catalyst packed with metal palladium prepared in step 丨To prepare a catalyst for producing acetic acid and ethyl acetate of. 29 · —A method for manufacturing a catalyst for manufacturing acetic acid and ethyl ethyl acetate, such as in the scope of application for patent No. 18, which includes the following steps and steps: The first step is a step in which (a) a metal Palladium and (c) at least one element selected from the group consisting of elements of Groups 14, 15 and 16 of the Periodic Table are loaded on a carrier to obtain a catalyst filled with metal palladium. Step 2-step, (B) at least one compound selected from the group consisting of: inorganic acids and their salts are loaded on a metal-palladium-filled catalyst prepared in the first step to obtain an acetic acid and acetic acid; Ethyl catalyst. 1 A method for manufacturing a catalyst for the production of acetic acid and ethyl acetate, as described in item 18 of the patent, comprising the following first steps. The first step is a step, in which the rhenium metal is loaded on a carrier. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 public 90 491835) 6. The scope of the patent application is to obtain a catalyst filled with metal palladium; The second step is a step in which (b) at least one Chemicals from the following groups: Inorganic salts and salts thereof and (c) at least one element selected from the group: elements from groups 14, 15, and 16 of the periodic table are filled in the first! It is filled with gold and catalyzed to obtain a catalyst for producing acetic acid, acetic acid, and ethyl ester. 31.- A catalyst for producing acetic acid and ethyl acetate, such as the scope of application for item 19 The manufacturing method includes the following first steps: The first step is a step in which at least one of thallium metal and thallium is selected from the elements of the following group: Periodic Table 6, 7, 8, 9, 10, u : Elements of Group 12 are loaded on the carrier A catalyst for preparing metal palladium; 2nd step is a step in which (b) at least one compound selected from the group consisting of: inorganic acid and its salts are packed in the packing prepared in step 丨There is a metal catalyst on one of the catalysts to prepare a catalyst for di-acid and ethyl acetate. 32.-A method for manufacturing a catalyst for the production of acetic acid and ethyl warm ethyl acetate, such as the scope of application for item 19 , Which includes the following steps · Step 1 I Acetic acid paper size applies Chinese National Standard (CNS) A4 specifications (210X297 public love) .'Order · (Please read the precautions on the back before filling this page) 491835 A8 B8 C8 D8 VI. Patent application scope is a step in which (a) metal palladium is packed on a carrier, and the stomach is made into a kind Catalyst loaded with metal palladium; ^ Step 2 is a step in which (b) at least one compound selected from the group consisting of inorganic acids and salts thereof and (d) at least one element selected from the group consisting of: · Periodic Table 6, 7, 8, 9, 10, imi2_ Φ elements are loaded on a metal-palladium-filled catalyst prepared in the first step to prepare a catalyst for the production of acetic acid and ethyl acetate . 33 · -A method for manufacturing a catalyst for manufacturing acetic acid and ethyl acetate in the patent scope of item 2G, which includes the following first steps: The first step is a step in which the metallurgical period, (C ) At least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table and ⑷ at least one element selected from the group consisting of groups 7: 2, 9, 10, 11 and 12 of the periodic table The elements are loaded on a carrier to prepare a catalyst filled with metal palladium; the second step is a step in which at least one compound selected from the group consisting of: 无机 inorganic acids and salts thereof is loaded in the first step The obtained catalyst was packed with a metal palladium catalyst to prepare a catalyst for Z production, obituary and ethyl acetate. 34.-If you want to manufacture acetic acid and ethyl acetic acid according to item 20 of the scope of patent application (please read the precautions on the back before filling this page), you can ... This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 > < 297 Public Love) -92 491835 The patented patented Fanyuan Ethyl Acetate catalyst manufacturing method includes the following 2nd step: Step 1 is a step in which (a) metal palladium is loaded on a support to prepare a catalyst filled with metal palladium; step 2 is a step in which at least one compound selected from the group consisting of rhenium : Inorganic acids and their salts, (C) at least one element selected from the group consisting of elements of groups 14, 15 and 16 of the periodic table and at least one element selected from the following group ... Elements of Groups 7, 7, 10, 11 and 12 are packed on the catalyst loaded with metal palladium prepared in the step ′ to obtain a catalyst for the purpose of producing acetic acid and ethyl acetate. 35. A method for manufacturing a catalyst for manufacturing acetic acid and ethyl acetate, as described in the patent, which includes the following steps of the first step: Step 1 is a step in which the metal Select at least one element from the following groups with a το element of Groups 6, 7, 8, 9, i0, and 12 of the periodic table on a carrier to prepare a catalyst filled with metal palladium; 2. The second step is a step in which at least one compound selected from the group consisting of: inorganic acids and salts thereof and (c) at least one member selected from the following groups. The paper size is applicable to the Chinese National Standard (CNS) A4 specification ( (210X297 mm) 2 elements: Periodic Table Groups 14, 15 and 16 elements are packed on a catalyst filled with metal catalysts in the 1st cymbal to obtain seeds for the production of acetic acid and ethyl acetate. The catalyst. 36. A method for manufacturing a catalyst for the production of acetic acid and ethyl acetate, such as in the scope of the patent, including the following step: 'The first step is a step in which the rhenium metal is mixed with rhenium At least one element selected from the group consisting of elements from Groups 14, 15 and 16 of the Periodic Table to be filled on the chastity body to obtain a metal-filled catalyst. Step 2 is a step in which at least A compound selected from the group consisting of inorganic acids and their salts and (d) at least one element selected from the group consisting of: Periodic Table 6, 7, 8, 9, 10, lmm_ The catalyst prepared in the step is packed with a metal palladium catalyst to prepare a catalyst for producing acetic acid and ethyl acetate. 37. A method for producing acetic acid and ethyl acetate, comprising reacting ethanol with oxygen in the presence of a catalyst for producing acetic acid and ethyl acetate as described in items 17 to 27 of the patent application scope. . 38. The method of claim 37, wherein ethanol and oxygen react in the presence of water. 39. The method according to item 37 or 38 of the scope of patent application, in which ethanol and oxygen 491835 A8 B8 C8 6. Application scope of patent application ^ ~~ ^ ----- It is a reaction in a liquid phase. 40. As described in claim 37 or 38, the ethanol and oxygen react in a gas phase. For example, the method of claim 40 in the patent application range, wherein the concentration of water in the starting gas is 0_1 to 50% by volume. 42. The method of claim 37, wherein the starting gas or liquid system is blended with acetaldehyde and / or diethyl ether and / or ethylene, and then reacted. 43. The method of claim 37, wherein the starting gas or liquid system is blended with acetic acid and then reacted. 44. The method according to item 43 of the scope of patent application, wherein after the acetic acid and ethyl acetate are prepared by the reaction of ethanol and oxygen, ethyl acetate is separated from the reaction mixture for collection, and the acetic acid is returned Into the reaction system for reaction. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 95 ............. I Meal -.............. Order .. .... (Please read the notes on the back before filling this page)