JP2005095873A - Process for producing catalyst for production of acetic acid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for producing a catalyst for the production of acetic acid, which is used in a process for producing acetic acid from ethylene and oxygen, has palladium and at least one compound selected from the group consisting heteropolyacids and salts thereof deposited on a support and can ensure production of acetic acid with higher activity and less reduction in the performance accompanying changes in aging. <P>SOLUTION: This carrier-supported catalyst is used in a process for producing acetic acid by reacting ethylene with oxygen in a gas phase and contains palladium (a) and at least one compound (b) selected from the group consisting of heteropolyacids and salts thereof as indispensable components. Palladium is separately deposited at least through two steps in this process for producing the carrier-supported catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a catalyst for producing acetic acid in which at least one selected from palladium, heteropolyacids and salts thereof used for producing acetic acid from ethylene and oxygen in the gas phase is supported on a carrier, and the production method And a method for producing acetic acid using the catalyst.

  The present invention particularly relates to a method for producing a catalyst in which at least one member selected from the group consisting of palladium, heteropolyacids and salts thereof is supported on a carrier, wherein palladium is supported in a plurality of steps. It is related with the manufacturing method of the catalyst for acetic acid production characterized by controlling the loading state of this.

  Regarding the method for producing acetic acid from ethylene in one step, many proposals have been made because it has many advantages in the industrial production process and economically. Specifically, for example, from a liquid phase one-step oxidation method using a redox catalyst of a metal ion pair such as palladium-cobalt or palladium-iron (French Patent No. 1448361), palladium-phosphoric acid or sulfur-containing modifier. Gas phase one-step oxidation method using a catalyst comprising a three-group oxygen compound (Japanese Examined Patent Publication No. Sho 46-006763) using a catalyst comprising the following catalyst (Japanese Patent Laid-Open Nos. 47-013221 and 51-029425) Etc. have been proposed. Further, as a method for producing acetic acid using a catalyst containing a palladium compound and a heteropolyacid, Japanese Patent Application Laid-Open No. 54-57488 proposes a gas-phase one-step oxidation method using a catalyst comprising a phosphovanadomolybdate salt. ing.

  Further, recently, a process for producing acetic acid from ethylene and oxygen in a single gas phase using a catalyst containing at least one compound selected from the group consisting of palladium, heteropolyacids and salts thereof (JP-A-7-89896). Japanese Patent Laid-Open No. 9-67298). According to the method using this catalyst, acetic acid can be obtained in a relatively high yield. A catalyst containing at least one compound selected from the group consisting of palladium, heteropolyacids and salts thereof for synthesizing acetic acid from ethylene and oxygen has an extremely high activity due to the interaction between palladium metal and heteropolyacid. It expresses that it exhibits selectivity and exhibits excellent acetic acid production activity and selectivity.

  Further, a catalyst used in the production of acetic acid by directly oxidizing ethylene using a catalyst having at least one compound selected from the group consisting of palladium, heteropolyacid and salts thereof as an essential component, and production of the catalyst A method and an improved method for producing acetic acid using the catalyst have been proposed in JP-A Nos. 11-34712, 2000-308830, WO00 / 051725, WO00 / 061535, and the like.

  As a conventionally proposed method for producing acetic acid from ethylene and oxygen in a single gas phase, a catalyst containing at least one compound selected from the group consisting of palladium, heteropolyacids and salts thereof is carried out on an industrial scale. Shows sufficient performance above. However, if further improvement in catalytic activity can be achieved, it is advantageous in terms of economy.

  A conventionally disclosed method for producing a catalyst in which at least one compound selected from the group consisting of palladium and heteropolyacids and salts thereof is supported on a carrier basically includes the following steps. Yes.

1st process The process which carries | supports palladium on a support | carrier, and manufactures a palladium supported catalyst 2nd process The process of carrying | supporting heteropoly acid or heteropoly acid salt on the palladium supported catalyst obtained at the 1st process, and obtaining the catalyst for acetic acid manufacture Above-mentioned In the method, the palladium supporting step is preferably performed once, and the step of supporting the heteropolyacid or heteropolyacid salt in a separate step following the step of producing the palladium-supported catalyst is a feature. .

  Further, in the step of obtaining the palladium-supported catalyst in the first step, it is advantageous to obtain an egg shell type palladium catalyst. The egg shell type refers to a type in which the support position of palladium in the support is outside the support. It can be inferred that the reason why the egg shell type is effective is that the reaction substrate hardly diffuses in the center of the catalyst support or in the inner region, and the metal component supported in or near the center region does not greatly contribute to the reaction. . Further, JP-A-7-89896 describes that a method for producing a palladium-supported catalyst characterized by including an alkali treatment step such as sodium metasilicate is advantageous in order to obtain an egg shell type palladium catalyst. Yes. Furthermore, in Japanese Patent Application Laid-Open No. 2000-308830, a method for producing a palladium-supported catalyst is advantageous, which includes a step of treating with a barium salt such as barium hydroxide in order to obtain an egg shell type palladium catalyst. It is described.

  That is, conventionally disclosed methods for producing a catalyst for acetic acid production are characterized in that palladium is supported on a carrier to obtain a palladium-supported catalyst, and then a heteropolyacid or heteropolyacid salt is subsequently supported.

French Patent No. 1448361 JP 47-013221 A JP-A-51-029425 Japanese Examined Patent Publication No. 46-006763 JP 54-57488 A JP-A-7-89896 JP-A-9-67298 Japanese Patent Laid-Open No. 11-347412 JP 2000-308830 A WO00 / 051725 WO00 / 061535 JP 2000-308830 A

  The present invention is a catalyst for producing acetic acid, in which at least one compound selected from the group consisting of palladium, heteropolyacids and salts thereof used in a method for producing acetic acid from ethylene and oxygen is supported on a carrier, It is an object of the present invention to provide a method capable of producing a catalyst for producing acetic acid, which can obtain acetic acid with high activity and further has a low performance deterioration with time.

  In the reaction of obtaining acetic acid from ethylene and oxygen in the presence of a catalyst consisting of palladium and heteropolyacid, it is unlikely that palladium and heteropolyacid are working alone, and high selectivity and productivity due to their interaction. It is thought that it is expressed.

  As a conventional method for producing a catalyst for acetic acid production in which at least one compound selected from the group selected from the group consisting of palladium and heteropolyacids and salts thereof for obtaining acetic acid from ethylene and oxygen is supported on the carrier, A method is disclosed in which palladium and a heteropolyacid or heteropolyacid salt are supported at different timings. More specifically, it comprises a step of supporting palladium on a carrier and a step of supporting a heteropolyacid or heteropolyacid salt on the obtained palladium-supported catalyst. In this case, in a microscopic state, the two are not completely uniformly in close contact with each other and may not interact. In particular, in the disclosed process for producing a catalyst for acetic acid production, a palladium-carrying catalyst is produced by immersing in an alkali treatment liquid and then performing a reduction treatment. The position is of egg shell type. On the other hand, the heteropolyacid or heteropolyacid salt is uniformly supported on the entire support. Therefore, in the central part of the carrier, there is a region where there is no palladium and only the heteropolyacid or heteropolyacid salt is present. That is, the heteropolyacid or heteropolyacid salt supported on the center may not contribute to the reaction.

  In order to further improve the catalyst performance, the present inventors paid attention to the positions of palladium and a heteropolyacid or heteropolyacid salt in a catalyst for producing acetic acid produced by a conventionally disclosed catalyst production method.

  The present inventors have intensively studied to solve such a problem. As a result, surprisingly, at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof used in a method for producing acetic acid from ethylene and oxygen is used as an essential component. As described above, in the method for producing a carrier-supported catalyst, it is possible to give higher productivity by using the method for producing a catalyst for acetic acid production, characterized in that palladium is supported in at least two steps. The present inventors have found that a catalyst for acetic acid production in which the change in catalyst performance with time is suppressed is obtained.

  That is, this invention (I) uses at least 1 sort (s) chosen from the group which consists of (a) palladium and (b) heteropolyacid and those salts used for the manufacturing method of the acetic acid which makes ethylene and oxygen react in a gaseous phase. In the method for producing a carrier-supported catalyst containing a compound, the method for producing a catalyst for producing acetic acid is characterized in that palladium is supported in at least two steps.

  Furthermore, the present invention (II) is used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase, and is at least one selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof. In the method for producing a carrier-supported catalyst comprising the compound of (c) and at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te, palladium is supported in at least two steps. This is a method for producing a catalyst for producing acetic acid.

  Next, the present invention (III) uses at least one selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase. Compound, (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te and (d) selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn In the method for producing a carrier-supported catalyst containing at least one element, palladium is supported in at least two steps, and the method for producing a catalyst for acetic acid production is characterized.

  And this invention (IV) uses at least 1 sort (s) chosen from the group which consists of (a) palladium, (b) heteropolyacid, and those salts used for the manufacturing method of the acetic acid which makes ethylene and oxygen react with a gaseous phase. Compound, (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te, (d) selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn In the method for producing a carrier-supported catalyst containing at least one element and (e) at least one element selected from the group consisting of V and Mo, palladium is supported in at least two steps. A method for producing a catalyst for producing acetic acid.

  The present invention (V) is an acetic acid production catalyst obtained by the method for producing an acetic acid production catalyst of the present invention (I) to (IV).

  Furthermore, the present invention (VI) is a method for producing acetic acid using the catalyst for producing acetic acid of the present invention (V).

  Therefore, this invention consists of the following matters, for example.

  [1] A carrier-supported type comprising at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase A method for producing a catalyst for acetic acid production, characterized in that palladium is supported in at least two steps in the catalyst production method.

  [2] The method for producing a catalyst for producing acetic acid according to the above [1], comprising the following first step and second step.

First Step (a) A step of obtaining palladium on a carrier by supporting palladium on a carrier Second step A palladium-carrying catalyst obtained in the first step comprises (a) palladium and (b) a heteropolyacid and salts thereof. A step of obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of [3] (a) palladium, (a) used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase; b) a carrier-supported catalyst comprising at least one compound selected from the group consisting of heteropolyacids and salts thereof and (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te. In the production method, a method for producing a catalyst for producing acetic acid, wherein palladium is supported in at least two steps.

  [4] The method for producing a catalyst for producing acetic acid according to the above [3], comprising the following first step and second step.

Step 1 Step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of (a) palladium and (c) Sn, Pb, Bi, Sb and Te on the support. By supporting at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof on the palladium-supported catalyst containing the group (c) element obtained in the process, Step for obtaining catalyst [5] The method for producing a catalyst for producing acetic acid according to the above [3], comprising the following first step and second step.

1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process is made into (a) palladium, (b) heteropoly acid, and those salts. And (c) a catalyst containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te is supported to obtain a catalyst for producing acetic acid. Step [6] The method for producing a catalyst for producing acetic acid according to the above [3], comprising the following first to third steps.

1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process consists of (c) Sn, Pb, Bi, Sb, and Te. (C) A step of obtaining a palladium-supported catalyst containing a group element by supporting a compound containing at least one element selected from the group 3rd step (c) A palladium support containing a group element obtained in the second step (7) A step of obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof on the catalyst. (A) at least one compound selected from the group consisting of palladium, (b) heteropolyacids and salts thereof, (c) Sn, Pb , Bi, Sb and Te, at least one element selected from the group consisting of, and (d) a carrier comprising at least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn A method for producing a catalyst for acetic acid production, characterized in that in the method for producing a supported catalyst, palladium is supported in at least two steps.

  [8] The method for producing a catalyst for producing acetic acid according to the above [7], comprising the following first step and second step.

First Step (a) At least one element selected from the group consisting of (a) palladium, (c) Sn, Pb, Bi, Sb and Te and (d) Cr, Mn, Fe, Ru, Co, Cu, A step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of Au and Zn. Second step (c) A palladium support containing the group element (d) and the (d) group element obtained in the first step. Step of obtaining acetic acid production catalyst by supporting at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacid and salts thereof on the catalyst [9] The following first step and The method for producing a catalyst for producing acetic acid according to the above [7], comprising a second step.

Step 1 Step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of (a) palladium and (c) Sn, Pb, Bi, Sb and Te on the support. The palladium-carrying catalyst containing the (c) group element obtained in the step, (a) at least one compound selected from the group consisting of palladium, (b) heteropolyacid and salts thereof, and (d) Cr, Mn, Fe A step of obtaining a catalyst for producing acetic acid by supporting a compound containing at least one element selected from the group consisting of Ru, Co, Cu, Au and Zn [10] The following first step and second step: The method for producing a catalyst for producing acetic acid according to the above [7], comprising:

First Step (a) Palladium and (d) At least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn is supported on the support to obtain a palladium-supported catalyst. Step 2 Step (d) The palladium-supported catalyst containing the group element obtained in Step 1 is combined with (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, and ( c) A step of obtaining a catalyst for producing acetic acid by supporting a compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te. [11] The following first step and second step The method for producing a catalyst for producing acetic acid according to the above [7], comprising:

1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process is made into (a) palladium, (b) heteropoly acid, and those salts. At least one compound selected from the group consisting of: (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te; and (d) Cr, Mn, Fe, Ru, Co, Cu A step of obtaining a catalyst for producing acetic acid by supporting a compound containing at least one element selected from the group consisting of Au and Zn. [12] The following first step to third step are included. The manufacturing method of the catalyst for acetic acid manufacture as described in said [7].

First Step (a) Palladium and (d) At least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn is supported on the support to obtain a palladium-supported catalyst. Step 2 Step (d) A palladium-supported catalyst containing a group element obtained in Step 1 is combined with (c) a compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te. Step of obtaining a palladium-supported catalyst containing (c) group element and (d) group element by loading Third step (c) A palladium-supported catalyst containing (c) group element and (d) group element obtained in the second step (A) Palladium and (b) A step of obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of heteropolyacids and salts thereof [13] The following first to second steps [3] The method for producing a catalyst for producing acetic acid according to the above [7], comprising 3 steps.

1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process consists of (c) Sn, Pb, Bi, Sb, and Te. (C) A step of obtaining a palladium-supported catalyst containing a group element by supporting a compound containing at least one element selected from the group 3rd step (c) A palladium support containing a group element obtained in the second step The catalyst includes (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, (d) a group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn. A step of obtaining a catalyst for producing acetic acid by supporting at least one element selected from [14] (a) Paradium used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase. (B) at least one compound selected from the group consisting of heteropolyacids and salts thereof, (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te, (d) Support-supported catalyst comprising at least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn and (e) at least one element selected from the group consisting of V and Mo The method for producing a catalyst for acetic acid production, comprising carrying out palladium loading in at least two steps.

  [15] The method for producing a catalyst for producing acetic acid according to the above [14], comprising the following first step and second step.

First Step (a) At least one element selected from the group consisting of (a) palladium, (c) Sn, Pb, Bi, Sb and Te and (d) Cr, Mn, Fe, Ru, Co, Cu, A step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of Au and Zn. Second step (c) A palladium support containing the group element (d) and the (d) group element obtained in the first step. The catalyst contains (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, and (e) a compound containing at least one element selected from the group consisting of V and Mo. A step of obtaining a catalyst for producing acetic acid by carrying it. [16] The method for producing a catalyst for producing acetic acid according to the above [14], comprising the following first step and second step.

Step 1 Step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of (a) palladium and (c) Sn, Pb, Bi, Sb and Te on the support. The palladium-carrying catalyst containing the group element (c) obtained in the step is composed of (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, (d) Cr, Mn, Acetic acid is obtained by supporting a compound containing at least one element selected from the group consisting of Fe, Ru, Co, Cu, Au and Zn and (e) at least one element selected from the group consisting of V and Mo. Step for obtaining catalyst for production [17] The method for producing a catalyst for production of acetic acid according to [14] above, comprising the following first step and second step.

First Step (a) Palladium and (d) At least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn is supported on the support to obtain a palladium-supported catalyst. Step 2 Step (d) The palladium-supported catalyst containing the group element obtained in the first step is combined with at least one compound selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof, ( c) A compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te and (e) at least one element selected from the group consisting of V and Mo. Step for obtaining production catalyst [18] The method for producing a catalyst for production of acetic acid according to [14] above, which comprises the following first step and second step.

1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process is made into (a) palladium, (b) heteropoly acid, and those salts. At least one compound selected from the group consisting of: (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te; (d) Cr, Mn, Fe, Ru, Co, Cu And (e) a step of obtaining a catalyst for producing acetic acid by supporting a compound containing at least one element selected from the group consisting of Au and Zn and (e) at least one element selected from the group consisting of V and Mo. [19] The method for producing a catalyst for producing acetic acid as described in [14] above, which comprises the following first to third steps.

First Step (a) Palladium and (d) At least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn is supported on the support to obtain a palladium-supported catalyst. Step 2 Step (d) A palladium-supported catalyst containing a group element obtained in Step 1 is combined with (c) a compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te. Step of obtaining a palladium-supported catalyst containing (c) group element and (d) group element by loading Third step (c) A palladium-supported catalyst containing (c) group element and (d) group element obtained in the second step (A) at least one compound selected from the group consisting of palladium, (b) heteropolyacids and salts thereof, and (e) at least one element selected from the group consisting of V and Mo. Accordingly, the above-mentioned [14] process for the production of acetic acid catalyst for production, wherein the containing obtain acetic acid production catalyst process [20] The following first to third steps.

1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process consists of (c) Sn, Pb, Bi, Sb, and Te. (C) A step of obtaining a palladium-supported catalyst containing a group element by supporting a compound containing at least one element selected from the group 3rd step (c) A palladium support containing a group element obtained in the second step The catalyst includes (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, (d) a group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn. And (e) a step of obtaining a catalyst for producing acetic acid by supporting at least one element selected from the group consisting of V and Mo. The above [2], [5], [6], [11], [13], [18] or [20], further comprising the following steps 1-1 to 1-3: Of producing a catalyst for the production of acetic acid.

Step 1-1: (a) Step of supporting a palladium compound on a carrier to obtain a palladium-supported catalyst Step 1-2: Step of immersing the palladium-supported catalyst obtained in Step 1-1 in an aqueous alkaline solution Step 3 A step of obtaining a metal palladium supported catalyst by reducing the palladium supported catalyst obtained in Step 1-2 [22] The first step further comprises the following Step 1-1 to Step 1-3: The method for producing a catalyst for producing acetic acid according to claim [4], [9] or [16].

Step 1-1: Step of obtaining a palladium-supported catalyst by supporting (a) a palladium compound and (c) a compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te on a support. Step 1-2 Step of immersing the palladium-supported catalyst containing the group element (c) obtained in step 1-1 in an alkaline aqueous solution Step 1-3 Step (c) Group element obtained in step 1-2 (C) A step of obtaining a metal palladium-supported catalyst containing a group element by reducing a palladium-supported catalyst containing [23] The first step further includes the following steps 1-1 to 1-3: The method for producing a catalyst for producing acetic acid according to claim [10], [12], [17] or [19].

Step 1-1: A palladium-supported catalyst carrying (a) a palladium compound and (d) at least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au, and Zn on a carrier. Step 1-2 Step of immersing the palladium-supported catalyst containing the group element (d) obtained in Step 1-1 in an alkaline aqueous solution Step 1-3 Obtained in Step 1-2 (d ) A step of reducing a palladium-supported catalyst containing a group element to obtain a metal palladium-supported catalyst containing a group element (d) [24] The first step is further performed by the following steps 1-1 to 1-3: The process for producing a catalyst for producing acetic acid according to [8] or [15], comprising a step.

Step 1-1: On the support, (a) palladium compound, (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te, and (d) Cr, Mn, Fe, Ru, Co Step of supporting at least one element selected from the group consisting of Cu, Au and Zn to obtain a palladium-supported catalyst Step 1-2 Step (c) Group element obtained in Step 1-1 and Step (d) Step of immersing palladium-supported catalyst containing group element in alkaline aqueous solution 1-3 Step By reducing palladium-supported catalyst containing group element (c) and (d) group element obtained in step 1-2 (C) A step of obtaining a metal palladium supported catalyst containing a group element and (d) group element [25] (b) The heteropolyacids and salts thereof are selected from the following heteropolyacids and salts thereof: Above The manufacturing method of the catalyst for acetic acid manufacture in any one of [1]-[24].

1-12-phosphotungstic acid: H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O
1-12-silicotungstic acid: H ₄ [SiW ₁₂ O ₄₀ ] · nH ₂ O
(In the formula, n represents an integer of 0 to 40)
[26] A catalyst for producing acetic acid obtained by the method for producing a catalyst for producing acetic acid according to any one of [1] to [25].

  [27] A method for producing acetic acid, comprising reacting ethylene and oxygen in a gas phase in the presence of the catalyst for producing acetic acid obtained by the method for producing a catalyst for producing acetic acid according to [26].

  According to the present invention, acetic acid can be obtained with higher activity in the method for producing acetic acid from ethylene and oxygen, and further, a catalyst for producing acetic acid can be obtained which has a low performance deterioration with time.

  A preferred embodiment of the present invention will be described below.

Invention (I)-Method for Producing Catalyst for Acetic Acid Production First, the method for producing the catalyst for acetic acid production of the invention (I) will be described.

  The method for producing a catalyst for producing acetic acid according to the present invention (I) is used in the method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase, and is from the group consisting of (a) palladium and (b) heteropolyacid and salts thereof. In the method for producing a carrier-supported catalyst containing at least one selected compound, palladium is supported in at least two steps, and the method for producing a catalyst for acetic acid production is characterized.

  Preferably, this manufacturing method includes the following first step and second step.

First step (a) A step of obtaining palladium on a support by supporting palladium on a carrier Second step A palladium-supported catalyst obtained in the first step comprises (a) a palladium compound, (b) a heteropolyacid, and their Step of obtaining acetic acid production catalyst by supporting at least one compound selected from the group consisting of salts of the present invention (I)-Step 1 Step 1 is the step of supporting (a) palladium on a carrier. This is a step of obtaining a palladium-supported catalyst.

  There is no restriction | limiting in the support | carrier used for this invention (I). Any porous material generally used as a carrier may be used. Silica, silica-alumina, diatomaceous earth, montmorillonite, titania and the like are preferable, and silica is more preferable. Moreover, there is no restriction | limiting in particular in the shape of a support | carrier. Specific examples include powders, spheres, and pellets, but are not limited thereto.

  Further, the size of the carrier particles used in the present invention (I) is not particularly limited. When used in a fixed bed tubular reactor, if the support is spherical, the particle diameter is preferably in the range of 1-10 mm, more preferably 2-8 mm. When the reaction is carried out with a tubular reactor filled with a catalyst, if the particle diameter is smaller than 1 mm, a large pressure loss occurs when the gas is circulated, and there is a possibility that the gas cannot be circulated effectively. On the other hand, if the particle diameter is larger than 10 mm, the reaction gas cannot be diffused to the inside of the catalyst, and the catalytic reaction may not proceed effectively. The pore structure of the carrier preferably has a pore diameter of 1 to 1000 nm, more preferably 2 to 800 nm.

  In the present invention (I), the carrier-supported catalyst is a catalyst in which at least one compound selected from the group consisting of (a) palladium, (b) heteropolyacid or a salt thereof is held on the carrier. Show.

  The supported (a) palladium in the present invention (I) may be in any state. For example, it may be a compound or element as it is. That is, it may be an ionic or zero-valent metallic state, but is preferably a metallic state.

  In the first step, (a) the palladium raw material compound is not particularly limited. Specific examples include halides such as metal palladium and palladium chloride, organic acid salts such as palladium acetate, nitrates such as palladium nitrate, palladium oxide, sodium tetrachloropalladate, potassium tetrachloropalladate, and the like. A complex having an organic compound such as acetonate, nitrile, or ammonium as a ligand may be used. Particularly preferred are sodium tetrachloropalladate, potassium tetrachloropalladate, palladium nitrate and the like.

  When obtaining an eggshell-type palladium-supported catalyst, (a) the method for supporting palladium on the carrier is not particularly limited as long as the result is an eggshell-type palladium-supported catalyst. The egg shell type catalyst is one in which the active component is distributed in the carrier particles / molded body, and the active component is present only on the outer surface of the carrier particle or molded body. Specifically, for example, a method in which the raw material compound is dissolved in a suitable solvent such as water or acetone, an inorganic acid or an organic acid such as hydrochloric acid, nitric acid, acetic acid, or a solution thereof and directly supported on the surface layer, And a method of indirectly supporting. Examples of the direct supporting method include an impregnation method and a spray method. Examples of the method of indirectly supporting can include a method of reducing after carrying out an alkali treatment.

  (A) The operation of converting palladium to a metal state may be performed after (a) the catalyst supporting palladium is isolated, or may be performed subsequent to the supporting operation. Further, it is possible to reduce only a part of the supported palladium without reducing it. Examples of the reducing agent used include hydrazine, hydrogen, and ethylene.

  It is preferable that the palladium is supported on the carrier in a so-called “egg shell type”.

  In the first step, in order to obtain an egg shell type palladium-supported catalyst, the following method can be preferably exemplified as an example.

Step 1-1: (a) Step of supporting a palladium compound on a carrier to obtain a palladium-supported catalyst Step 1-2: Step of immersing the palladium-supported catalyst obtained in Step 1-1 in an aqueous alkaline solution Step 3 Step of reducing the palladium-supported catalyst obtained in Step 1-2 to obtain a metal-palladium-supported catalyst The alkaline aqueous solution used in Step 1-2 is sodium hydroxide, sodium metasilicate and / or water. It may be an alkaline aqueous solution such as barium oxide. In this step, a part or all of the palladium compound can be converted into an oxide or a hydroxide.

  Step 1-3 is a step of reducing the palladium compound to metal palladium after converting the palladium compound into an oxide or hydroxide. (A) The operation of converting palladium to a metal state may be performed after (a) the catalyst supporting palladium is isolated, or may be performed subsequent to the supporting operation. Examples of the reducing agent used include hydrazine, hydrogen, and ethylene.

  As described above, (a) a palladium-supported catalyst can be obtained.

Second step of the present invention (I) The second step of the present invention (I) is carried out by adding the palladium-supported catalyst obtained in the first step to (a) palladium and (b) a heteropolyacid and a salt thereof. A step of obtaining a catalyst for producing acetic acid by supporting at least one selected compound is a step of obtaining a catalyst for producing acetic acid. That is, in this step, a palladium component is further supported on the palladium supported catalyst.

  (A) Palladium used in the second step of the present invention (I) is not particularly limited. Specific examples include organic acid salts such as palladium acetate, nitrates such as palladium nitrate, and complexes having an organic compound such as acetylacetonate, nitrile, and ammonium as a ligand. Preferably, a palladium compound that does not contain chlorine and dissolves in an acidic aqueous solution is preferable, and examples thereof include palladium nitrate and palladium acetate. When a catalyst for the production of acetic acid is produced using a halide such as palladium chloride, chloropalladate, sodium tetrachloropalladate, etc., if the catalyst is used without sufficiently removing the halogen from the catalyst, Halogen may flow through the reaction tube and cause corrosion. It is difficult to completely remove the halogen by a normal method, and it is not preferable because, for example, it is necessary to wash the catalyst with an aqueous solution or to heat at a high temperature for a long time.

  The heteropolyacid (b) used in the second step of the present invention (I) is preferably a heteropolyacid composed of tungsten as a poly atom. Examples of the hetero atom include, but are not limited to, phosphorus, silicon, boron, aluminum, germanium, titanium, zirconium, cerium, cobalt, and chromium. Preferred are phosphorus, silicon, and boron. Specific heteropolyacids preferably include silicotungstic acid, phosphotungstic acid, and borotungstic acid. More preferred are silicotungstic acid and phosphotungstic acid. Further, a heteropolyacid represented by the following chemical formula known as a Keggin type structure is practically preferable, but all the heteropolyacids on the catalyst may not have this structure.

1-12-phosphotungstic acid: H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O
1-12-silicotungstic acid: H ₄ [SiW ₁₂ O ₄₀ ] · nH ₂ O
(In the formula, n represents an integer of 0 to 40)
Furthermore, the salt of (b) heteropolyacid used in the catalyst of the present invention (I) is a metal salt in which some or all of the hydrogen atoms of the acid formed by condensation of two or more inorganic oxygen acids are substituted, or It is an onium salt. The metal in which the hydrogen atom of the heteropoly acid is substituted is preferably at least one element selected from the group consisting of Group 1, Element 2, Group 11, and Group 13 elements in the periodic table. Examples of the onium salt of the acid include ammonium salts. Among these heteropolyacid salts, metal salts of lithium, sodium, potassium, cesium, magnesium, barium, copper, gold and gallium are particularly preferable.

  Further, as a salt of heteropolyacid that is preferable in terms of catalytic performance and practical use, phosphotungstic acid lithium salt, phosphotungstic acid sodium salt, phosphotungstic acid copper salt, silicotungstic acid lithium salt, silicotungstic acid sodium salt and Although the copper salt of silicotungstic acid can be mentioned, it is not limited to these.

  Examples of the method for supporting at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof on a carrier include means such as impregnation method and spray method. Is not to be done. As the solvent used in the impregnation, a solvent capable of dissolving at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof is preferable. Water, an organic solvent and a mixture thereof are used. Can be used. Preferably, water and alcohol are used.

  Further, the carrying order may be separate or simultaneous. Preferably, a method of simultaneously supporting for the purpose of obtaining a contact effect between palladium and a heteropolyacid or heteropolyacid salt is preferable.

Examples of the method of supporting simultaneously include a method of simultaneously supporting on a carrier as a homogeneous solution containing at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof. More specifically, an appropriate solvent such as water or acetone, or an inorganic acid or organic acid such as hydrochloric acid, nitric acid or acetic acid is selected from the group consisting of (a) palladium compounds and (b) heteropolyacids and salts thereof. There is a method in which at least one compound is dissolved to obtain a homogeneous solution, which is then impregnated into a carrier and then dried. In addition, after obtaining a heteropolyacid palladium salt prepared from at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacid and salts thereof, the heteropolyacid palladium salt is dissolved in an appropriate solvent. And may be supported on a carrier. Preferred heteropolyacids for use in heteropolyacid palladium salts include:
1-12-phosphotungstic acid: H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O
1-12-silicotungstic acid: H ₄ [SiW ₁₂ O ₄₀ ] · nH ₂ O
(In the formula, n represents an integer of 0 to 40)
Is mentioned. The heteropolyacid palladium salt can be obtained, for example, by preparing an aqueous solution in which palladium nitrate and the heteropolyacid are dissolved and drying.

  The catalyst may be dried after supporting at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacid and salts thereof as a solution, for example, vacuum treatment at a low temperature. And a method of removing the solvent by heat treatment with a hot air dryer.

  After loading, if necessary, the catalyst may be subjected to a reduction treatment. The reduction treatment is preferably performed in the gas phase, and is not particularly limited as long as it is a general reduction condition.

  Examples of the reducing agent include hydrogen, ethylene, methanol, CO and the like, but are not particularly limited. Preferably, they are hydrogen and ethylene.

  When the reduction treatment is performed, the temperature is not particularly limited, but it is preferable to heat the catalyst obtained in the first step to around 50 to 350 ° C. More preferably, it is 100-300 degreeC. If the reaction is performed at 350 ° C. or higher, the heteropolyacid may be decomposed, which is not preferable.

  Although it is practically advantageous that the processing pressure is 0.0 to 3.0 MPa (gauge pressure) in terms of equipment, there is no particular limitation. More preferably, it is the range of 0.1-1.5 MPa (gauge pressure).

  When circulating a gaseous reducing agent, it may be carried out at any reducing agent concentration, and nitrogen, carbon dioxide, or a rare gas can be used as a diluent as required. Further, the reduction may be carried out in the presence of vaporized water in the presence of ethylene, hydrogen or the like. Alternatively, the catalyst prepared in the first step may be charged into a reaction system reactor and reduced with ethylene, and oxygen may be further introduced to produce acetic acid from ethylene and oxygen.

The mixed gas containing the gaseous reducing agent is preferably passed through the catalyst at a space velocity (hereinafter referred to as SV) of 10 to 15000 hr ⁻¹ , particularly 100 to 8000 hr ⁻¹ in a standard state.

  The treatment format is not particularly limited, but it is practically advantageous to employ a fixed bed in which a reaction tube having corrosion resistance is filled with the above-described catalyst.

  As described above, the catalyst for producing acetic acid can be obtained by the production method of the present invention (I).

  The method for producing a catalyst for producing acetic acid according to the present invention (I) is characterized in that the palladium supporting step is performed a plurality of times. Preferably, it is preferable to use a method in which palladium and a heteropolyacid or heteropolyacid salt are simultaneously supported in the second step after obtaining a palladium-supported catalyst by supporting palladium on a carrier in the first step.

  The ratio of palladium supported in the first step and the second step is preferably preferably the amount of palladium supported in the first step / the amount of palladium supported in the second step = 30/1 to 1/1, more preferably 25. / 1 to 2/1. If the amount of palladium supported in the first step / the amount of palladium supported in the second step is higher than 30/1, the amount of palladium supported in the second step is small, so the effect may be reduced. On the other hand, when the ratio is lower than 1/1, since the proportion of palladium supported inside the carrier increases, there is a possibility that a predetermined reaction amount cannot be obtained due to the diffusion rate limiting of the reaction substrate.

  In the catalyst for producing acetic acid obtained by the production method of the present invention (I), (a) palladium and (b) a catalyst in which at least one compound selected from heteropolyacids and salts thereof is held on a carrier ( The composition of a) and (b) is not particularly limited. Preferably, (a) :( b) = 0.5 to 2.5% by mass: 5 to 50% by mass is preferable, and (a) :( b) = 1.0 to 2.5% by mass: More preferable results are obtained at 10 to 40% by mass.

  The supported amount and composition ratio of the metal element and the heteropolyacid contained in the catalyst for producing acetic acid produced in the present invention (I) are determined by a high frequency inductively coupled plasma emission spectrometer (hereinafter referred to as ICP), fluorescent X-ray analysis ( Hereinafter, it can be accurately obtained by chemical analysis such as atomic absorption spectrometry.

  For example, after a certain amount of catalyst is pulverized in a mortar or the like to obtain a uniform powder, the catalyst powder is added to an acid such as hydrofluoric acid or aqua regia, heated and stirred, and dissolved to obtain a uniform solution. Next, the solution is diluted to an appropriate concentration with pure water to obtain a solution for analysis. A method for quantitative analysis of the solution by ICP can be mentioned.

Invention (II) -Method for Producing Acetic Acid Production Catalyst A method for producing the acetic acid production catalyst of the invention (II) will be described.

  The method for producing a catalyst for producing acetic acid according to the present invention (II) is used from the group consisting of (a) palladium, (b) heteropolyacid and salts thereof used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase. In a carrier-supported catalyst comprising at least one selected compound and (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te (hereinafter abbreviated as “(c) group element”) The method for producing a catalyst for producing acetic acid is characterized in that the loading of palladium is carried out in at least two steps.

Preferably, in the production method, the following first step and second step: first step: (a) palladium and (c) group element supported on a support to obtain a palladium-supported catalyst second step first step The catalyst for acetic acid production is obtained by supporting at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof on the palladium-supported catalyst containing the (c) group element obtained in (1). Or the following first step and second step: first step: (a) a step of obtaining palladium on a support by supporting palladium on a carrier; second step: a palladium-supported catalyst obtained in the first step; A catalyst for producing acetic acid is obtained by supporting at least one compound selected from the group consisting of a) palladium, (b) heteropolyacids and salts thereof, and (c) a compound containing a group element. The first step to the third step as described below or the first step The first step (a) A step of obtaining palladium-supported catalyst by supporting palladium on the carrier Second step The palladium-supported catalyst obtained in the first step (c) (C) Step of obtaining a palladium-supported catalyst containing a group element by supporting a compound containing a group element Third step (a) Palladium-supported catalyst containing a group element obtained in the second step And (b) a step of obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of heteropolyacids and salts thereof.

  In the first step, in order to obtain an egg shell type palladium-supported catalyst, the following method can be preferably exemplified as an example.

Step 1-1 Step of supporting a compound containing (a) a palladium compound and (c) group element on a carrier to obtain a palladium-supported catalyst Step 1-2 Step (c) Group obtained in Step 1-1 Step of immersing palladium-supported catalyst containing element in alkaline aqueous solution 1-3 step By reducing palladium-supported catalyst containing group element (c) obtained in step 1-2, (c) group element is obtained. The present invention (II) is a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase, and is used from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof. This is a method for producing a carrier-supported catalyst containing at least one selected compound and (c) group element.

  The present invention (II) is a method of further adding the (c) group element to the catalyst production method of the present invention (I).

  That is, (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof and a carrier are the same as in the present invention (I). The same applies to the method of supporting the carrier.

  The (c) group element used in the present invention (II) is most preferably Te.

  There is no restriction | limiting in particular as a raw material compound of the (c) group element used by this invention (II). For example, the element itself, or chloride salts, nitrates, acetates, phosphates, sulfates, oxides, etc. containing the elements, and organic substances such as acetylacetonate and nitrile are used as ligands. A complex etc. are also mentioned.

  (C) There is no restriction | limiting in particular about the timing which carries a group element on a support | carrier. For example, it may be supported simultaneously with (a) palladium, or (b) simultaneously with at least one compound selected from the group consisting of heteropolyacids and salts thereof, or independently. Preferably, (a) a method of supporting palladium independently after supporting it, or (b) a method of simultaneously supporting at least one compound selected from the group consisting of heteropolyacids and salts thereof is preferable.

  The ratio of palladium supported in the first step and the second step is the same as in the present invention (I).

In the catalyst for acetic acid production obtained by the production method of the present invention (II), (a) palladium, (b) at least one compound selected from heteropolyacids and salts thereof, and (c) group elements are held on a carrier. The composition of (a), (b) and (c) in the catalyst is not particularly limited. Preferably, (a) :( b) :( c) = 0.5 to 2.5% by mass: 5 to 50% by mass: 0.05 to 3.0% by mass is preferable as the mass% in the entire catalyst. In particular, (a) :( b) :( c) = 1.0 to 2.5% by mass: 10 to 40% by mass: 0.08 to 1.0% by mass gives more preferable results.
Invention (III)-Method for Producing Acetic Acid Production Catalyst A method for producing the acetic acid production catalyst of the invention (III) will be described.

  The method for producing a catalyst for producing acetic acid according to the present invention (III) is used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase, and comprises a group consisting of (a) palladium, (b) heteropolyacid and salts thereof. At least one selected compound, (c) group element and (d) at least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn (hereinafter referred to as “(d) A method for producing a catalyst for acetic acid production, characterized in that a carrier-supported catalyst containing a "group element" is carried out in at least two steps.

Preferably, in the production method, the following first step and second step: first step: (a) palladium, (c) group element and (d) group element are supported on a support to obtain a palladium-supported catalyst. Second Step The palladium-carrying catalyst containing the (c) group element and the (d) group element obtained in the first step is at least one selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof. Step of obtaining acetic acid production catalyst by supporting seed compound, or the following first step and second step First step (a) Palladium and (c) Group element are supported on a support, and palladium supported catalyst Step 2 Step 2 The palladium-carrying catalyst containing the group element (c) obtained in Step 1 is at least one compound selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof, and ( ) A step of obtaining a catalyst for producing acetic acid by supporting a compound containing a group element or the following first step and second step: First step: (a) Palladium and (d) a group element are supported on a support, Step of obtaining palladium-supported catalyst Second step At least one selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof is used as the palladium-supported catalyst containing the (d) group element obtained in the first step. The step of obtaining a catalyst for producing acetic acid by supporting a compound containing a seed compound and (c) group element, or the following first step and second step, first step: (a) palladium is supported on the carrier, Step of obtaining palladium-supported catalyst Second step The palladium-supported catalyst obtained in the first step is combined with at least one compound selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof. , (C) A step of obtaining a catalyst for producing acetic acid by supporting a compound containing a group element and (d) group element, or the following first step to third step: First step: (a) Palladium and ( d) Step of supporting a group element to obtain a palladium-supported catalyst Second step By supporting a compound containing (c) a group element on the palladium-supported catalyst containing the (d) group element obtained in the first step. , (C) A step of obtaining a palladium-supported catalyst containing a group element and (d) group element Third step A palladium-supported catalyst containing the (c) group element and (d) group element obtained in the second step is subjected to (a Step of obtaining acetic acid production catalyst by supporting at least one compound selected from the group consisting of :) palladium and (b) heteropolyacid and salts thereof, or the following first step to third step: first step Support (A) Parajiu A step of obtaining a palladium-supported catalyst by supporting the catalyst 2nd step A palladium-supported catalyst obtained in the first step by supporting a compound containing the (c) group element, thereby supporting the palladium containing the (c) group element. Step 3 for obtaining a catalyst Step 3) The palladium-carrying catalyst containing group element (c) obtained in Step 2 is at least one selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof. The method includes a step of obtaining a catalyst for producing acetic acid by supporting a compound, the (d) group element.

  In the first step, in order to obtain an egg shell type palladium-supported catalyst, the following method can be preferably exemplified as an example.

Step 1-1 Step (a) A step of obtaining a palladium-supported catalyst by supporting a palladium compound and a group (d) group element on a carrier. Step 1-2 A unit (d) obtained in Step 1-1 is included. Step of immersing a palladium-supported catalyst in an alkaline aqueous solution Step 1-3: Metal palladium containing (d) group element by reducing the palladium-supported catalyst containing (d) group element obtained in Step 1-2. Step of obtaining a supported catalyst The present invention (III) is a method in which (d) group element is further added to the catalyst production method of the present invention (II).

  That is, (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, (c) group elements and carriers are the same as in the present invention (II). The same applies to the method of supporting the carrier.

  The group (d) element used in the present invention (III) is preferably Cr, Au and Zn, and more preferably Au and Zn.

  There is no restriction | limiting in particular as a raw material compound of the (d) group element used by this invention (III). For example, the element itself, or chloride salts, nitrates, acetates, phosphates, sulfates, oxides, etc. containing the elements, and organic substances such as acetylacetonate and nitrile are used as ligands. A complex etc. are also mentioned.

  (D) There is no particular limitation on the timing at which the group elements are supported on the carrier. For example, it may be supported simultaneously with (a) palladium, or (b) simultaneously with at least one compound selected from the group consisting of heteropolyacids and salts thereof, or independently. (A) It is preferable to carry out simultaneously with the loading of palladium.

  The ratio of palladium supported in the first step and the second step is the same as in the present invention (I).

  In the catalyst for producing acetic acid obtained by the production method of the present invention (III), at least one compound selected from (a) palladium, (b) heteropolyacid and salts thereof, (c) group element and (d) group The composition of (a), (b), (c) and (d) in the catalyst in which the element is supported on the support is not particularly limited. Preferably, as mass% in the whole catalyst, (a) :( b) :( c) :( d) = 0.5-2.5 mass%: 5-50 mass%: 0.05-3.0 % By mass: 0.05 to 3.0% by mass is preferable, and (a): (b): (c): (d) = 1.0 to 2.5% by mass: 10 to 40% by mass: 0.0. 08-1.0 mass%: A more preferable result is given in 0.08-1.0 mass%.

Invention (IV)-Method for Producing Acetic Acid Production Catalyst A method for producing the acetic acid production catalyst of the invention (IV) will be described.

  The method for producing a catalyst for producing acetic acid according to the present invention (IV) is used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase, from the group consisting of (a) palladium, (b) heteropolyacid and salts thereof. At least one selected compound, (c) group element, (d) group element, and (e) at least one element selected from the group consisting of V and Mo (hereinafter referred to as “(e) group element”) A method for producing a catalyst for producing acetic acid, comprising: carrying a supported catalyst in which palladium is supported in at least two steps.

Preferably, in the production method, the following first step and second step: first step: (a) palladium, (c) group element and (d) group element are supported on a support to obtain a palladium-supported catalyst. Second Step The palladium-carrying catalyst containing the (c) group element and (d) group element obtained in the first step is at least one selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof. A step of obtaining a catalyst for producing acetic acid by supporting a compound containing a seed compound and a group element (e), or the following first step and second step, first step: (a) palladium and group (c) Step of supporting element to obtain palladium-supported catalyst Second step (c) The palladium-supported catalyst containing group element obtained in the first step is composed of (a) palladium, (b) heteropolyacid and salts thereof. Chosen from the group A step of obtaining a catalyst for producing acetic acid by supporting at least one compound, a compound containing a group element (d) and a group element (e), or the following first step and second step: First step: a) Step of supporting palladium and (d) group element to obtain a palladium-supported catalyst Second step The palladium-supported catalyst containing (d) group element obtained in the first step is added to (a) palladium, (b) A step of obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of heteropolyacids and salts thereof, a compound containing (c) group element and (e) group element, or the following first Step and Second Step First Step (a) A step of obtaining a palladium-supported catalyst by supporting palladium on a carrier Second step A palladium-supported catalyst obtained in the first step is subjected to (a) palladium, (b) heteropoly And a step of obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of salts thereof, (c) group element, (d) group element and (e) group element, or The following 1st process-3rd process 1st process (a) Palladium and the (d) group element are carry | supported to a support | carrier, The process which obtains a palladium carrying catalyst 2nd process (d) group obtained at the 1st process A step of obtaining a palladium-supported catalyst containing (c) group element and (d) group element by supporting a compound containing (c) group element on a palladium-supported catalyst containing element. A palladium-supported catalyst containing (c) group element and (d) group element, at least one compound selected from the group consisting of (a) palladium, (b) heteropolyacid and salts thereof, and (e) group element By carrying Step for obtaining a catalyst for producing acetic acid or the following first to third steps: First step (a) A step of obtaining palladium-supported catalyst by supporting palladium on a carrier Second step Palladium obtained in the first step (C) A step of obtaining a palladium-supported catalyst containing a group element by supporting a compound containing a group element (c) on a supported catalyst. Third step (c) A palladium support containing a group element obtained in the second step. A catalyst for acetic acid production by supporting at least one compound selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof, (d) group element and (e) group element on the catalyst It includes the process of obtaining.

  In the first step, in order to obtain an egg shell type palladium-supported catalyst, the following method can be preferably exemplified as an example.

Step 1-1 Step of supporting a (a) palladium compound, (c) group element and (d) group element on a carrier to obtain a palladium-supported catalyst Step 1-2 Obtained in Step 1-1 ( c) Step of immersing palladium-supported catalyst containing group element and (d) group element in alkaline aqueous solution 1-3 step palladium containing (c) group element and (d) group element obtained in step 1-2 A step of obtaining a metal palladium-supported catalyst containing the (c) group element and the (d) group element by reducing the supported catalyst. The present invention (IV) includes (e) ) A method of further adding group elements.

  That is, (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, (c) group element, (d) group element and carrier, the present invention (III) and It is the same. The same applies to the method of supporting the carrier.

  There is no restriction | limiting in particular as a raw material compound of the (e) group element used by this invention (IV). For example, the element itself, or chloride salts, nitrates, acetates, phosphates, sulfates, oxides, etc. containing the elements, and organic substances such as acetylacetonate and nitrile are used as ligands. A complex etc. are also mentioned.

  (E) The raw material compound of the group element may be a heteropolyacid containing V and Mo. Specific examples include the following heteropolyacids, but there is no particular limitation.

Phosphormolybdic acid: H ₃ [PMo ₁₂ O ₄₀ ] · nH ₂ O
Silicomolybdic acid: H ₄ [SiMo ₁₂ O ₄₀ ] · nH ₂ O
Caivanadotungstic acid: H _{4 + x} [SiV _x W _12-x O ₄₀ ] · nH ₂ O
Phosphorbanadotungstic acid: H _{3 + x} [PV _x W _12-x O ₄₀ ] · nH ₂ O
Phosphovanadomolybdic acid: H _{3 + x} [PV _x Mo _12-x O ₄₀ ] · nH ₂ O
Caivanadomolybdic acid: H _{4 + x} [SiV _x Mo _12-x O ₄₀ ] · nH ₂ O
Si-molybdotungstic acid: H ₄ [SiMo _x W _12-x O ₄₀ ] · nH ₂ O
Phosphorus molybdate de tungstic _{acid: H 3 [PMo x W 12} -x O 40] · nH 2 O
(Where n is a positive integer)
Preferably, phosphomolybdic acid, phosphovanadomolybdic acid, silicomolybdic acid, and silicomolybdic molybdic acid are used.

  (E) There is no particular limitation on the timing at which the group elements are supported on the carrier. For example, it may be supported simultaneously with (a) palladium, or (b) simultaneously with at least one compound selected from the group consisting of heteropolyacids and salts thereof, or independently. Preferably, (b) a method of simultaneously supporting at least one compound selected from the group consisting of heteropolyacids and salts thereof is preferable.

  The ratio of palladium supported in the first step and the second step is the same as in the present invention (I).

  In the catalyst for producing acetic acid obtained by the production method of the present invention (IV), (a) palladium, (b) at least one compound selected from heteropolyacids and salts thereof, and (c) group element, (d) There is no particular limitation on the composition of (a), (b), (c), (d) and (e) in the catalyst in which the group element and (e) group element are held on the support. Preferably, as mass% in the whole catalyst, (a) :( b) :( c) :( d) :( e) = 0.5-2.5 mass%: 5-50 mass%: 0.05 -3.0% by mass: 0.05-3.0% by mass: 0.05-1.0% by mass is preferable, and in particular, (a) :( b) :( c) :( d) :( e) = 1.0 to 2.5% by mass: 10 to 40% by mass: 0.08 to 1.0% by mass: 0.08 to 1.0% by mass: more preferable results at 0.1 to 0.8% by mass give.

  The present invention (V) is an acetic acid production catalyst obtained by the method for producing an acetic acid production catalyst of the present invention (I) to (IV).

  In the catalyst of the present invention (V), according to the conventionally disclosed technique, palladium is an egg shell type in the support position of each catalyst component in the support, and the heteropolyacid or heteropolyacid salt is uniform. Therefore, there is no palladium in the center of the carrier, and there is a region where only the heteropolyacid or heteropolyacid salt exists, and palladium and the heteropolyacid or heteropolyacid salt do not interact closely. That is, the supported heteropolyacid or heteropolyacid salt may not be effectively used. Therefore, it was intended to effectively use the catalyst component by carrying out the palladium supporting step, which is a method for producing the acetic acid production catalyst of the present invention (I) to (IV), twice or more.

  In order to know the loading position in the carrier of palladium and heteropolyacid or heteropolyacid salt, for example, elemental analysis by X-ray microprobe method (hereinafter referred to as “EPMA”) can be mentioned. EPMA is a device that irradiates a solid substance with an electron probe focused on a micron order, and performs elemental analysis, morphology observation, etc. using characteristic X-rays, reflected electrons, secondary electrons, etc. generated from the minute parts It is. Details of EPMA are described in “EPMA Electronic Probe Microanalyzer” (written by Kurouchi Goro, published by Technical Institute, March 30, 2002, first edition, first print).

  In the catalyst for producing acetic acid of the present invention (V), elements contained in the support, such as palladium, heteropolyacid or heteropolyacid salt (for example, tungsten) are analyzed by EPMA, so that palladium and heteropolyacid or heteropolyacid salt You can know how closely.

Invention (VI)-Method for Producing Acetic Acid Using Acetic Acid Production Catalyst Next, the invention (VI) will be described.

  The present invention (VI) is a process for producing acetic acid from ethylene and oxygen using the acetic acid production catalyst of the present invention (V).

  In the method for producing acetic acid of the present invention (VI), the reaction temperature for producing acetic acid by reacting ethylene with oxygen is not particularly limited. Preferably it is 100-300 degreeC, More preferably, it is 120-250 degreeC. Moreover, although it is practically advantageous that reaction pressure is 0.0-3.0 MPa (gauge pressure) from the point of an installation, there is no restriction | limiting in particular. More preferably, it is the range of 0.1-1.5 MPa (gauge pressure).

  In the method for producing acetic acid of the present invention (VI), the gas supplied to the reaction system contains ethylene and oxygen, and if necessary, nitrogen, carbon dioxide or a rare gas can be used as a diluent.

  With respect to the total amount of the supply gas, ethylene is in an amount of 5 to 80% by volume, preferably 8 to 50% by volume, and oxygen is 1 to 15% by volume, preferably 3 to 12% by volume. The amount is supplied to the reaction system.

  Further, in this reaction system, when water is present in the reaction system, it is remarkably effective in improving acetic acid production activity and selectivity and maintaining the activity of the catalyst. The water vapor is preferably contained in the reaction gas in the range of 1 to 50% by volume, more preferably 5 to 40% by volume.

  In the method for producing acetic acid of the present invention (VI), it is preferable to use a high-purity raw material ethylene, but it may be mixed with lower saturated hydrocarbons such as methane, ethane and propane. In addition, oxygen can be supplied in a form diluted with an inert gas such as nitrogen or carbon dioxide, for example, in the form of air. However, when the reaction gas is circulated, it is generally high concentration, preferably 99% or more. It is advantageous to use oxygen.

The reaction gas mixture, at standard conditions, SV10~15000hr ^{- 1,} preferably especially passed through the catalyst at 300~8000hr ^-1.

  There is no restriction | limiting in particular as a reaction format, For example, formats, such as a fixed bed and a fluidized bed, can be taken. Preferably, it is practically advantageous to employ a fixed bed in which the above-described catalyst is packed in a reaction tube having corrosion resistance.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, these examples show an outline of the present invention and are not intended to limit the present invention only to these examples.

Pretreatment of carrier All the carriers used in the examples were dried at 110 ° C under air for 4 hours as a pretreatment.

Use of water The water used in the examples is all deionized water.

Use of carrier The carrier used in the examples is a silica carrier [BET specific surface area of 148 m ² / g, bulk density of 405 g / l, 5 mmφ].

Use of raw material compounds An aqueous solution of sodium chloropalladate [Na ₂ PdCl ₄ ] in hydrochloric acid (hereinafter referred to as HCl) and an aqueous nitric acid solution of palladium nitrate [Pd (NO ₃ ) ₂ ] used in the examples were manufactured by NV Chemcat Co., Ltd. belongs to. Silicotungstic acid 26 hydrate [H ₄ SiW ₁₂ O ₄₀ · 26H ₂ O] is manufactured by Nippon Inorganic Chemical Industry Co., Ltd.

Components in each catalyst Elemental analysis of metal elements and heteropolyacids contained in the catalyst for producing acetic acid obtained in Example 1 and Comparative Example 1 was performed as follows. That is, each acetic acid production catalyst is dissolved in aqua regia and / or a mixture of hydrofluoric acid and aqua regia by heat treatment in the presence of pressure, and each component is completely extracted, and ICP (Seiko Instruments Inc.) Measured by SPS-1700). The mass% of each component in the catalyst is shown.

Example 1
Sodium chloropalladate (3.56 g) and zinc chloride [manufactured by Wako Pure Chemicals: ZnCl ₂ ] (54 mg) were mixed and made up with ion-exchanged water to prepare 45 ml of an aqueous solution (solution A). This A solution was impregnated on a silica carrier (40 g) to absorb the whole amount. Next, the solution was added to an aqueous solution (90 ml) of sodium metasilicate nonahydrate [manufactured by Wako Pure Chemicals: Na ₂ SiO ₃ .9H ₂ O] (8.0 g) and allowed to stand at room temperature for 20 hours. Next, hydrazine monohydrate [manufactured by Wako Pure Chemicals: N ₂ H ₄ · H ₂ O] (6.5 g) was added to this, and after gently stirring, the mixture was allowed to stand at room temperature for 4 hours to obtain metallic palladium. Reduced to Thereafter, the catalyst was collected by filtration and decanted, then transferred to a glass column with a stopcock, and washed with pure water flowing for 40 hours. Next, it was dried at 110 ° C. for 4 hours under an air stream to obtain a metal palladium supported catalyst containing Zn.

Next, 45 ml of an aqueous solution in which sodium tellurite [Wako Pure Chemicals: Na ₂ TeO ₃ ] (72 mg) was dissolved was prepared (B solution). The B solution was impregnated with the previously prepared metal palladium-supported catalyst and absorbed in its entirety. Subsequently, it was dried at 110 ° C. for 4 hours under an air stream to obtain a metal palladium supported catalyst containing Zn and Te.

  Furthermore, silicotungstic acid 26 hydrate (20.7 g) and palladium nitrate aqueous solution (0.067 g as Pd) were made into a uniform aqueous solution and made up to 45 ml (C solution). This C solution was impregnated with the previously prepared metal palladium-supported catalyst containing Zn and Te and absorbed in its entirety. Subsequently, the catalyst 1 for acetic acid manufacture was obtained by drying at 110 degreeC for 4 hours under airflow.

  As a result of ICP analysis, Pd in the catalyst is 1.73%, Au is 0.59%, Zn is 0.09%, Te is 0.13%, W is 22.9%, Mo is 0.09% It was recognized that

Comparative Example 1
Sodium chloropalladate (3.80 g) and zinc chloride [manufactured by Wako Pure Chemicals: ZnCl ₂ ] (54 mg) were mixed and diluted with ion-exchanged water to prepare 45 ml of an aqueous solution (solution A). This A solution was impregnated with silica support (40 g) and absorbed in its entirety. Next, it was added to an aqueous solution (90 ml) of sodium metasilicate nonahydrate [manufactured by Wako Pure Chemicals: Na ₂ SiO ₃ .9H ₂ O] (8.0 g) and allowed to stand at room temperature for 20 hours. Next, hydrazine monohydrate [manufactured by Wako Pure Chemicals: N ₂ H ₄ · H ₂ O] (6.5 g) was added to this, and after gently stirring, the mixture was allowed to stand at room temperature for 4 hours to obtain metallic palladium. Reduced to Thereafter, the catalyst was collected by filtration and decanted, then transferred to a glass column with a stopcock, and purified water was circulated for 40 hours for washing. Subsequently, it dried at 110 degreeC under air flow for 4 hours, and obtained the metal palladium carrying | support catalyst containing Zn.

Next, 45 ml of an aqueous solution in which sodium tellurite [Wako Pure Chemicals: Na ₂ TeO ₃ ] (72 mg) was dissolved was prepared (B solution). The B solution was impregnated with the previously prepared metal palladium-supported catalyst and absorbed in its entirety. Next, it was dried at 110 ° C. for 4 hours under an air stream to obtain a metal palladium supported catalyst containing Zn and Te.

  Furthermore, silicotungstic acid 26 hydrate (20.7 g) was made into a uniform aqueous solution and made up to 45 ml (C solution). This C solution was impregnated with the previously prepared metal palladium-supported catalyst containing Zn and Te and absorbed in its entirety. Subsequently, the catalyst 2 for acetic acid manufacture was obtained by drying for 4 hours at 110 degreeC under airflow.

  As a result of ICP analysis, Pd in the catalyst was 1.72%, Au was 0.59%, Zn was 0.09%, Te was 0.14%, W was 23.0%, Mo was 0.09% It was included.

Example 2 and Comparative Example 2
The catalyst for acetic acid production 1 and the catalyst for acetic acid production 2 obtained in Example 1 and Comparative Example 1 were each filled in a reaction tube (inner diameter 25 mm) made of SUS316 without diluting 5 ml, and the reaction peak temperature 220 of the catalyst layer. C., a reaction pressure of 0.8 MPaG (gauge pressure), and a gas mixed at a volume ratio of ethylene: oxygen: water: nitrogen = 10: 6: 15: 69 was introduced at a space velocity of 1800 hr.sup.- ¹ . A reaction for obtaining acetic acid from ethylene and oxygen was carried out.

  As an analysis method in the reaction, the entire amount of the outlet gas that passed through the catalyst packed bed was cooled, and the condensed reaction collection liquid was recovered and analyzed by gas chromatography. The uncondensed gas remaining without being condensed was measured for the total amount of the uncondensed gas that flowed out within the sampling time, a part of the uncondensed gas was taken out, and the composition was analyzed by gas chromatography. The produced gas was cooled, and the condensate and gas components after cooling were gas chromatographed (GC-14B, Shimadzu Corporation, FID detector: capillary column TC-WAX (length 30 m, inner diameter 0.25 mm, film thickness 0. 25 μm)).

  The activity of the catalyst was calculated as the mass of acetic acid produced per catalyst volume (liter) per hour (space time yield STY / unit g / hlcat).

  The reaction results are shown in FIG.

Measurement of silica (carrier), palladium and heteropolyacid (tungsten) distribution by EPMA A sample obtained by embedding the obtained catalyst for acetic acid in resin and polishing it was used with EPMA (JXA-8900 manufactured by JEOL Ltd.). The surface analysis of the cross section of the carrier particles was performed under the following conditions and measurement conditions. The results of processing the obtained surface analysis into line analysis data are shown in FIGS.

  FIG. 4 is a chart showing the results of EPMA analysis of tungsten of the acetic acid production catalyst obtained in Example 1, and FIG. 5 shows the results of EPMA analysis of Si of acetic acid production catalyst obtained in Comparative Example 1. FIG. 6 is a chart showing the results of EPMA analysis of Pd of the catalyst for producing acetic acid obtained in Comparative Example 1, and FIG. 7 is an EPMA of tungsten for the catalyst for producing acetic acid obtained in Comparative Example 1. The chart figure which shows an analysis result is shown.

Pretreatment Resin embedding: Cold embedding resin no. No. 105 no. Used with 105 curing agent.

  Cutting: Cutting with isomet (wet diamond cutter). Select a solvent that does not dissolve the heteropolyacid and / or heteropolyacid salt such as hexane.

  Vapor deposition: Platinum is used as the vapor deposition material.

EPMA analysis X-ray detector: wavelength dispersive detector (WDS)
Acceleration voltage: 15 kV
Irradiation current: 1 × 10 ⁻⁷ A

  The present invention is a carrier-supported catalyst comprising at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof, wherein the support of palladium is supported at least twice. High acetic acid productivity is obtained by using the catalyst for producing acetic acid obtained by the production method characterized in that it is extremely useful industrially.

FIG. 4 is a diagram showing a change with time of reaction in the production of acetic acid using the catalyst for producing acetic acid of Example 2 and Comparative Example 2. 2 is a chart showing the results of EPMA analysis of Si of the acetic acid production catalyst obtained in Example 1. FIG. 2 is a chart showing the EPMA analysis results of Pd of the acetic acid production catalyst obtained in Example 1. FIG. 2 is a chart showing EPMA analysis results of tungsten of the catalyst for producing acetic acid obtained in Example 1. FIG. 6 is a chart showing the results of EPMA analysis of Si of the catalyst for producing acetic acid obtained in Comparative Example 1. FIG. 6 is a chart showing the EPMA analysis result of Pd of the acetic acid production catalyst obtained in Comparative Example 1. FIG. 4 is a chart showing the EPMA analysis result of tungsten of the catalyst for producing acetic acid obtained in Comparative Example 1. FIG.

Claims (27)

  Production of a carrier-supported catalyst containing at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof used in a method for producing acetic acid in which ethylene and oxygen are reacted in the gas phase In the method, a method for producing a catalyst for producing acetic acid, wherein palladium is supported in at least two steps. The method for producing a catalyst for producing acetic acid according to claim 1, comprising the following first step and second step.
First Step (a) A step of obtaining palladium on a carrier by supporting palladium on a carrier Second step A palladium-carrying catalyst obtained in the first step comprises (a) palladium and (b) a heteropolyacid and salts thereof. A step of obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of   (A) at least one compound selected from the group consisting of palladium, (b) heteropolyacids and salts thereof, and (c) Sn, Pb, used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase. In a method for producing a carrier-supported catalyst containing at least one element selected from the group consisting of Bi, Sb, and Te, a catalyst for acetic acid production, wherein palladium is supported in at least two steps. Production method. The method for producing a catalyst for producing acetic acid according to claim 3, comprising the following first step and second step.
Step 1 Step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of (a) palladium and (c) Sn, Pb, Bi, Sb and Te on the support. By supporting at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof on the palladium-supported catalyst containing the group (c) element obtained in the process, Step of obtaining a catalyst The method for producing a catalyst for producing acetic acid according to claim 3, comprising the following first step and second step.
1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process is made into (a) palladium, (b) heteropoly acid, and those salts. And (c) a catalyst containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te is supported to obtain a catalyst for producing acetic acid. Process The method for producing a catalyst for producing acetic acid according to claim 3, comprising the following first to third steps.
1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process consists of (c) Sn, Pb, Bi, Sb, and Te. (C) A step of obtaining a palladium-supported catalyst containing a group element by supporting a compound containing at least one element selected from the group 3rd step (c) A palladium support containing a group element obtained in the second step A step of obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof on the catalyst.   (A) at least one compound selected from the group consisting of palladium, (b) heteropolyacids and salts thereof used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase, (c) Sn, Pb, Carrier support comprising at least one element selected from the group consisting of Bi, Sb and Te and (d) at least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn A method for producing a catalyst for acetic acid production, characterized in that in the method for producing a type catalyst, palladium is supported in at least two steps. The method for producing a catalyst for producing acetic acid according to claim 7, comprising the following first step and second step.
First Step (a) At least one element selected from the group consisting of (a) palladium, (c) Sn, Pb, Bi, Sb and Te and (d) Cr, Mn, Fe, Ru, Co, Cu, A step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of Au and Zn. Second step (c) A palladium support containing the group element (d) and the (d) group element obtained in the first step. A step of obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of (a) palladium and (b) heteropolyacids and salts thereof on the catalyst. The method for producing a catalyst for producing acetic acid according to claim 7, comprising the following first step and second step.
Step 1 Step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of (a) palladium and (c) Sn, Pb, Bi, Sb and Te on the support. The palladium-carrying catalyst containing the (c) group element obtained in the step, (a) at least one compound selected from the group consisting of palladium, (b) heteropolyacid and salts thereof, and (d) Cr, Mn, Fe Step of obtaining a catalyst for producing acetic acid by supporting a compound containing at least one element selected from the group consisting of Ru, Co, Cu, Au and Zn The method for producing a catalyst for producing acetic acid according to claim 7, comprising the following first step and second step.
First Step (a) Palladium and (d) At least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn is supported on the support to obtain a palladium-supported catalyst. Step 2 Step (d) The palladium-supported catalyst containing the group element obtained in Step 1 is combined with (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, and ( c) A step of obtaining a catalyst for producing acetic acid by supporting a compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te. The method for producing a catalyst for producing acetic acid according to claim 7, comprising the following first step and second step.
1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process is made into (a) palladium, (b) heteropoly acid, and those salts. At least one compound selected from the group consisting of: (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te; and (d) Cr, Mn, Fe, Ru, Co, Cu Step of obtaining a catalyst for producing acetic acid by supporting a compound containing at least one element selected from the group consisting of Au and Zn The method for producing a catalyst for producing acetic acid according to claim 7, comprising the following first to third steps.
First Step (a) Palladium and (d) At least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn is supported on the support to obtain a palladium-supported catalyst. Step 2 Step (d) A palladium-supported catalyst containing a group element obtained in Step 1 is combined with (c) a compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te. Step of obtaining a palladium-supported catalyst containing (c) group element and (d) group element by loading Third step (c) A palladium-supported catalyst containing (c) group element and (d) group element obtained in the second step And (a) palladium and (b) a process for obtaining a catalyst for producing acetic acid by supporting at least one compound selected from the group consisting of heteropolyacids and salts thereof. The method for producing a catalyst for producing acetic acid according to claim 7, comprising the following first to third steps.
1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process consists of (c) Sn, Pb, Bi, Sb, and Te. (C) A step of obtaining a palladium-supported catalyst containing a group element by supporting a compound containing at least one element selected from the group 3rd step (c) A palladium support containing a group element obtained in the second step The catalyst includes (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, (d) a group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn. A process for obtaining a catalyst for producing acetic acid by supporting at least one element selected from   (A) at least one compound selected from the group consisting of palladium, (b) heteropolyacids and salts thereof used in a method for producing acetic acid in which ethylene and oxygen are reacted in a gas phase, (c) Sn, Pb, At least one element selected from the group consisting of Bi, Sb and Te, (d) at least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn, and (e) A method for producing a catalyst for acetic acid production, characterized in that in the method for producing a carrier-supported catalyst containing at least one element selected from the group consisting of V and Mo, palladium is supported in at least two steps. . The method for producing a catalyst for producing acetic acid according to claim 14, comprising the following first step and second step.
First Step (a) At least one element selected from the group consisting of (a) palladium, (c) Sn, Pb, Bi, Sb and Te and (d) Cr, Mn, Fe, Ru, Co, Cu, A step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of Au and Zn. Second step (c) A palladium support containing the group element (d) and the (d) group element obtained in the first step. The catalyst contains (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, and (e) a compound containing at least one element selected from the group consisting of V and Mo. A step of obtaining a catalyst for producing acetic acid by loading The method for producing a catalyst for producing acetic acid according to claim 14, comprising the following first step and second step.
Step 1 Step of obtaining a palladium-supported catalyst by supporting at least one element selected from the group consisting of (a) palladium and (c) Sn, Pb, Bi, Sb and Te on the support. The palladium-carrying catalyst containing the group element (c) obtained in the step is composed of (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, (d) Cr, Mn, Acetic acid is obtained by supporting a compound containing at least one element selected from the group consisting of Fe, Ru, Co, Cu, Au and Zn and (e) at least one element selected from the group consisting of V and Mo. Process for obtaining production catalyst The method for producing a catalyst for producing acetic acid according to claim 14, comprising the following first step and second step.
First Step (a) Palladium and (d) At least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn is supported on the support to obtain a palladium-supported catalyst. Step 2 Step (d) The palladium-supported catalyst containing the group element obtained in the first step is combined with at least one compound selected from the group consisting of (a) palladium, (b) heteropolyacids and salts thereof, ( c) A compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te and (e) at least one element selected from the group consisting of V and Mo. Process for obtaining production catalyst The method for producing a catalyst for producing acetic acid according to claim 14, comprising the following first step and second step.
1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process is made into (a) palladium, (b) heteropoly acid and salts thereof. At least one compound selected from the group consisting of: (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te; (d) Cr, Mn, Fe, Ru, Co, Cu And (e) a step of obtaining a catalyst for producing acetic acid by supporting a compound containing at least one element selected from the group consisting of Au and Zn and (e) at least one element selected from the group consisting of V and Mo The method for producing a catalyst for producing acetic acid according to claim 14, comprising the following first to third steps.
First Step (a) Palladium and (d) At least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn is supported on the support to obtain a palladium-supported catalyst. Step 2 Step (d) A palladium-supported catalyst containing a group element obtained in Step 1 is combined with (c) a compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te. Step of obtaining a palladium-supported catalyst containing (c) group element and (d) group element by loading Third step (c) A palladium-supported catalyst containing (c) group element and (d) group element obtained in the second step (A) at least one compound selected from the group consisting of palladium, (b) heteropolyacids and salts thereof, and (e) at least one element selected from the group consisting of V and Mo. Accordingly, to obtain the acid catalyst for the production The method for producing a catalyst for producing acetic acid according to claim 14, comprising the following first to third steps.
1st process (a) The process which obtains a palladium carrying catalyst by carrying | supporting palladium on a support | carrier 2nd process The palladium carrying catalyst obtained at the 1st process consists of (c) Sn, Pb, Bi, Sb, and Te. (C) A step of obtaining a palladium-supported catalyst containing a group element by supporting a compound containing at least one element selected from the group 3rd step (c) A palladium support containing a group element obtained in the second step The catalyst includes (a) palladium, (b) at least one compound selected from the group consisting of heteropolyacids and salts thereof, (d) a group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au and Zn. And (e) a step of obtaining a catalyst for production of acetic acid by supporting at least one element selected from the group consisting of V and Mo. 21. The method for producing a catalyst for producing acetic acid according to claim 2, 5, 6, 11, 13, 18 or 20, wherein the first step further comprises the following steps 1-1 to 1-3.
Step 1-1: (a) Step of supporting a palladium compound on a carrier to obtain a palladium-supported catalyst Step 1-2: Step of immersing the palladium-supported catalyst obtained in Step 1-1 in an aqueous alkaline solution Step 3 Step of obtaining a palladium metal catalyst by reducing the palladium catalyst obtained in Step 1-2. The method for producing a catalyst for producing acetic acid according to claim 4, 9 or 16, wherein the first step further comprises the following steps 1-1 to 1-3.
Step 1-1: Step of obtaining a palladium-supported catalyst by supporting (a) a palladium compound and (c) a compound containing at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te on a support. Step 1-2 Step of immersing the palladium-supported catalyst containing the group element (c) obtained in step 1-1 in an alkaline aqueous solution Step 1-3 Step (c) Group element obtained in step 1-2 (C) A step of obtaining a metal palladium supported catalyst containing a group element by reducing a palladium supported catalyst containing The method for producing a catalyst for producing acetic acid according to claim 10, 12, 17 or 19, wherein the first step further comprises the following steps 1-1 to 1-3.
Step 1-1: A palladium-supported catalyst carrying (a) a palladium compound and (d) at least one element selected from the group consisting of Cr, Mn, Fe, Ru, Co, Cu, Au, and Zn on a carrier. Step 1-2 Step of immersing the palladium-supported catalyst containing the group element (d) obtained in Step 1-1 in an alkaline aqueous solution Step 1-3 Obtained in Step 1-2 (d (D) A step of obtaining a palladium metal-supported catalyst containing a group element by reducing a palladium-supported catalyst containing a group element (d) The method for producing a catalyst for producing acetic acid according to claim 8 or 15, wherein the first step further comprises the following steps 1-1 to 1-3.
Step 1-1: On the support, (a) palladium compound, (c) at least one element selected from the group consisting of Sn, Pb, Bi, Sb and Te, and (d) Cr, Mn, Fe, Ru, Co Step of supporting at least one element selected from the group consisting of Cu, Au and Zn to obtain a palladium-supported catalyst Step 1-2 Step (c) Group element obtained in Step 1-1 and Step (d) Step of immersing palladium-supported catalyst containing group element in alkaline aqueous solution 1-3 Step By reducing palladium-supported catalyst containing group element (c) and (d) group element obtained in step 1-2 , (C) a metal palladium supported catalyst containing a group element and (d) a group element (B) The method for producing a catalyst for producing acetic acid according to any one of claims 1 to 24, wherein the heteropolyacids and salts thereof are selected from the following heteropolyacids and salts thereof.
1-12-phosphotungstic acid: H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O
1-12-silicotungstic acid: H ₄ [SiW ₁₂ O ₄₀ ] · nH ₂ O
(In the formula, n represents an integer of 0 to 40)   The catalyst for acetic acid manufacture obtained by the manufacturing method of the catalyst for acetic acid manufacture in any one of Claims 1-25.   27. A method for producing acetic acid, comprising reacting ethylene and oxygen in a gas phase in the presence of the catalyst for producing acetic acid according to claim 26.

Images