ZA200108153B

ZA200108153B - Catalyst for production of acetic acid or acetic acid and ethyl acetate process for its production and process for production of acetic acid or acetic acid and ethyl acetate using it.

Info

Publication number: ZA200108153B
Application number: ZA200108153A
Authority: ZA
Inventors: Yoshiaki Obana; Hiroshi Uchida; Ken-Ichi Sano
Original assignee: Showa Denko Kk
Priority date: 1999-04-14
Filing date: 2001-10-04
Publication date: 2002-06-05

Description

DESCRIPTION

CATALYSES” FOR PRODUCTION OF ACETIC ACID OR ACETIC ACID AND

ETHYL : ,TATE, PROCESS FOR ITS PRODUCTION AND PRCOTESE FOR

PRODUCTION OF ACETIC ACID OR ACETIC ACID AND

ETHYL ACETATE USING IT

Cross Reference to Related Applications

This application is an application filed under 35

U.S.C. § 1ll(a) claiming benefit pursuant to 35 U.S.C. § 119(e) (1) of the filing dates of the Provisional )

Application No. 60/134,847, filed May 19, 1999, and the

Provisional Application No. 60/160,004, filed October 18, 1999, pursuant to 35 U.S.C. § 111(b).

Technical Field

The present invention relates to a catalyst for produc=ion of acetic acid or acetic acid and ethyl acetat: from ethanol and oxygen, to a process for its production and to a process for production of acetic acid or acetic acid and ethyl acetate using the catalyst.

Background Art

Processes for industrial production of acetic acid that have been realized include a process using oxidation of acetaldehyde, a process using a reaction of methanol and carbon monoxide and a process using oxidation of lower paraffins. Processes for industrial production of ethyl acetate that have been realized include an esterification reaction of ethanol and acetic acid, and a dimerization reaction of acetaldehyde. }

In recent years, various production prccesses for acetic acid using 2thanol as the starting material have been studied as an alterrative.

An example of a process for obtaining acetic acid from e:hanol in a single stage which employs copper oxide . as the main catalyst in combination with zinc oxide, . ot

-2- ‘ K \» chromium oxide and (chromium oxide-manganese oxide) {Japanese Unexamined Patent Publication No. 57-102835) has been disclosed. However, this process has been difficult to apply on an industrially practical scale because the reaction temperature is high at 260-360°C, and the acetic acid selectivity is not sufficient.

Oxidation processes with catalysts of platinum group metals, particularly palladium, have also been disclosed. ’ For example, acetic acid can be obtained by reacting a catalyst of metallic palladium or palladium loaded on a ° carrier such as silica or alumina (Japanese Examined

Patent Publication No. 48-19292, Brazil Patent BR- 9104562) with ethanol and oxygen. Palladium catalysts offer the advantage of a relatively low reaction temperature of 100-200°C. However, these processes have : all had.the drawback of abundant by-products such as acetaldehyde and carbon dioxide, which have lowered the i yield of the target acetic acid. ) Processes using metallic palladium-loaded catalysts have been disclosed as processes for obtaining ethyl acetate from ethanol by a single stage. For example, according to Kunugi and Matsuura et al. (Kogyo Kagaku

Zasshi, Vol.71, No.9, p.1517 (1968)), ethyl acetate is obtained from ethanol and oxygen in the vapor phase using a catalyst of metallic palladium loaded on a carrier of active carbon, y-alumina or the like. Ethyl acetate is also obtained from ethanol and oxygen using a metallic palladium/y-alumina catalyst (Brazil Patent BR-8901776).

However, these processes have had the disadvantage of a low conversion rate of ethanol and abundant by-products such as acetaldehyde, methane and carbon dioxide, which have lowered yields of the target ethyl acetate.

There has also been disclosed a catalyst including a palladium component and crystalline titanium pyrophosphate represented by (TiP,0,) (Japanese :

Unexamined Patent Publication No. 4-300851). Here,

+ WO 00/61535 PCT/JP00/022@03 improvement in ethyl acetate production activity has be=en reported by use of this binary catalyst having palladiu.m and titanium pyrophosphate as essential components, bot. . ever his process han iow ethyl acetate production : 5 activi. and selectivity, and is inadequate in practica 1 terms on an industrial scale.

On the other hand, processes employing palladium a.s the catalyst allow acetic acid and/or ethyl acetate to be obtained from ethanol and oxygen under relatively mild reaction conditions. Notwithstanding, for industrial scale production, a catalyst that is capable of ) catalyzing the reaction with even higher activity and higher selectivity is strongly desired.

Disclosure of Invention

It is an object of the present invention to provid. e a catalyst to be used for production of acetic acid or acetic acid and ethyl acetate from ethanol and oxygen, a process for its production, and a process for productiocen of acetic acid or acetic acid and ethyl acetate using t_he catalyst.

In order to achieve this object, the present inventors have conducted diligent research aimed at further increasing catalyst performance in a process fo r producing acetic acid or acetic acid and ethyl acetate from ethanol and oxygen using a palladium catalyst, and as a result we have completed the present invention upo n finding a catalyst with very low carbon 3ioxide selectivity, high activity and a long service life. 30 . Specifically, the invention (I) is a catalyst for production of acetic acid, which is a catalyst used in a process for production of acetic acid by reaction of ethanol and oxygen that comprises (a) metallic palladiu-m and (b) at least one element selected from the group : 35 consisting of Group 14 elements, Group 15 elements and

Group 16 elements of the Periodic Table, held on a carr. c.. a :

Co le The invention (II) is a catalyst for production of acetic acid, which is a catalyst used in a process for production of acetic acid by reaction of ethanol and oxygen that comprises (a) metallic palladium and (c) at least one element selected from the group consisting of

Group 6 elements, Group 7 elements, Group 8 elements,

Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elements of the Periodic Table, held on a

Co carrier. : a0 The invention (III) is a catalyst for production of. acetic acid, which is a catalyst used in a process for ‘production of acetic acid by reaction of ethanol and

Co oxygen that comprises (a) metallic palladium, (b) at least one element selected from the group consisting of as Group 14 elements, Group 15 elements and Group 16

BE + elements of the Periodic Table and (c) at least one "element selected from the group consisting of Group 6 ' elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Group : =0 12 elements of the Periodic Table, held on a carrier.

The invention (IV) is a process for production of a : catalyst according to any one of the inventions (I) to (III). : : The invention (V) is a process for production of : 25 acetic acid from ethanol and oxygen using a catalyst according to any one of the inventions (I) to (III).

The invention (VI) is a catalyst for production of acetic acid and ethyl acetate, which is a catalyst used in a process for production of acetic acid and ethyl acetate by reaction of ethanol and oxygen that comprises (a) metallic palladium and (b) at least one compound selected from the group consisting of inorganic acids and salts thereof.

The invention (VII) is a catalyst for production of acetic acid and ethyl acetate, which is a catalyst used in a process for production of acetic acid and ethyl acetate by reaction of ethanol and oxygen that comprises

Cy (a) metallic palladium, (b) at least one compound selected from the group consisting of inorganic acids and salts thereof, and (c) at least one element sel _ectel from the group consisting of Group 14 elements, roump 14 elements and Group 16 elerents of the Periodic Table.

The invention (VIII) is a catalyst for prcooduction of acetic acid and ethyl acetate, which is a catal_yst used in a process for production of acetic acid and ethyl acetate by reaction of ethanol and oxygen that comprises (a) metallic palladium, (b) at least one compound selected from the group consisting of inorganic acids and salts thereof, and (d) at least one element sel ected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elemants, Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elemermts of the

Periodic Table.

The invention (IX) is a catalyst for prodwaction of acetic acid and ethyl acetate, which is a catal_yst used in a process for production of acetic acid and ethyl acetate by reaction of ethanol and oxygen that comprises (a) metallic palladium, (b) at least one compovand selected from the group consisting of inorganic acids and salts thereof, (c) at least one element selected from the group consisting of Group 14 elements, Group 155 elements and Group 16 elements of the Periodic Table, ard (d) at least one element selected from the group cons®sting of

Group 6 elements, Group 7 elements, Group 8 esle=ments,

Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elements of the Periodic Table.

The invention (X) is a catalyst for production of acetic acid and ethyl acetate according to any one of the inventions (VI) to (IX), wherein the catalyst componen:s are held on a carrier.

The invention (XI) is a process for producction of z cataivst according to any one of the inventionss (VI) to (IX) that is not held on a carrier.

The invention (XII) is a process for production of ot :

+ the carrier-held catalyst of the invention (X).

The invention {XIII} is a process for production of acet=ic acid and ethyl acetate from ethanol and oxygen, usirag a catalyst according to any one of the inventions (VImM to (X).

Best= Mode for Carrying Out the Invention

A catalyst for production of acetic acid according "to t=he invention (I) will be explained first. The catamlyst of the invention (I) is a catalyst for : - production of acetic acid which is a catalyst used in a proc=ess for production of acetic acid by reaction of ethaunol and oxygen that comprises (a) metallic palladium and (b) at least one element selected: from_the group = cons:iisting of Group 14 elements, Group 15 elements and

Grou.p 16 elements of the Periodic Table (hereinafter may ° be referred to as group (b) element), held on a carrier.

The palladium contained in the catalyst of the inve ntion (I) is metallic palladium, and it has a valency 20° of 0 . The metallic palladium can be obtained by using a redu cing agent such as hydrazine, hydrogen or the like to redu ce a divalent and/or tetravalent palladium ion. All of t"he palladium need not be in a metallic state.

As the (b) Group 14 elements, Group 15 elements and

Grouzp 16 elements of the Periodic Table used for the invemntion (I) there may be mentioned selenium, tellurium, antimony, tin, bismuth and lead, but there is no restriction to these. Tellurium, selenium, bismuth and antizmony are particularly preferred for the group (b) eleme=nts in terms of catalyst performance and prac®ticality. :

The carrier used for the catalyst of the invention (I) =s not particularly restricted, and it may be a common porous substance commonly used for carriers. As prefeerred substances there may be mentioned silica, alum=ina, silica-alumina, diatomaceous earth, ’ montrs=norillonite and titania, or ion exchange resins,

-7 = polymer-based carriers, etc. with silica being most preferred. The form of the carrier is not particularly restricted. Specifically there may be mentioned the for .s of powcsr, spheres, pellets and tha like, but there is no limitation to these. The particle size of the carrier is not especially restricted. The particle size of the carrier is preferably from about 1 mm to about 10 mm, and more preferably 3 to 8 mm. When the reaction is carried out by packing the catalyst into a cylindrical reactor, a particle size that is under 1 mm will result in a large pressure loss when the gas flows through, and this may result in problems such as an inability to achieve effective gas circulation. If the particle size is greater than 10 mm, the reaction gas can no longer diffuse into the catalyst interior, and this may impede effective catalytic reaction.

The pore volume of the carrier is not particularly restricted. It is preferably a pore volume of from about 0.2 ml to about 2.0 ml, 6 and more preferably 0.3 to 1.5 ml, per gram of the carrier. There are no particular restrictions on the specific surface area of the carrier.

It is preferably a specific surface area of 20 to 800 m?, and more preferably 50 to 500 m?, per gram of the carrier. There are also no particular restrictions on the pore diameter of the carrier. It is preferably in the range 6f 1 to 2000 nm, and more preferably 3 to 800 nm.

The catalyst for production of acetic acid according to the invention (I) is a binary catalyst containing (a) 30 .-metallic palladium and a group (b) element. Although the structure of the catalyst has not been fully elucidated, the palladium is metallic palladium and the group (b) element is in the form of a metal, a compound or an alloy with metallic palladium, and when these are combined they : 35 are believed to exist very close together. The (a) meta’lic palladium and the group (b) element therefore interact expressing very high activity and selectivity. ow!

- The compositional ratio of the (a) metallic palladium and the one or more group (b) elements is preferably (a) 1 gram: (b) 0.005 to 10 grams, and more preferably (a) 1 gram: (b) 0.01 to 5 grams.

The loading amount of the (a) metallic palladium with respect to the carrier will differ depending on the © particle size and pore structure of the carrier, but it is normally preferred to be in the range of 0.05-10 wtd with respect to the carrier. Although the reaction will still proceed adequately even if the palladium loading . amount is under 0.1 wt%, this presents the risk of lower productivity. Also, although the reaction will still proceed adequately even if the amount is over 10 wt%, the high price of palladium renders this undesirable in * economic and practical terms. In practice, the range is more preferably 0.2-6 wt. Here, "tg" with respect to . the carrier refers to the value of the weight of the metallic palladium divided by the weight of the carrier.

The loading amount of the group (b) element with respect to the carrier will differ depending on the particle size and pore structure of the carrier, but it is preferably in the range of 0.0001-3 wt%, and more preferably in the range of 0.001-2.0 wt%, with respect to the carrier. Here, "wt%" with respect to the carrier refers to the value of the weight of the group (b) element divided by the weight of the carrier.

The amount of the components in the catalyst according to the invention (I) can be measured in the following manner. After pulverizing a prescribed amount of the catalyst with a mortar or the like into a uniform powder, it is added to an acid such as hydrofluoric acid or agua regia and dissolved by heating and stirring to prepare a homogeneous solution. The solution is then quantitatively analyzed with a plasma emission analyzer apparatus (for example, an $PS-1700 manufactured by Seiko

Electronic Industries, KK.). The precision of the ’ - apparatus can be easily adjusted with commercially available standard reagents of different elements, and repeatable quantitation is possible.

A catalyst for production of acetic acid according toc the invention (II) will now be explained. The catalyst of the invention (II) is a catalyst for production of acetic acid which is a catalyst used in a process for production of acetic acid by reaction of ethanol and oxygen that comprises (a) metallic palladium and (c) at least one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 ) elements and Group 12 elements of the Periodic Table (hereinafter may be referred to as group (c) element), held on a carrier.

The (a) metallic palladium in the catalyst of the invention (II) is the same as for the catalyst of the invention (I). The carrier is also the same as for the catalyst of the invention (I).

The (c) Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elements of the Periodic Table used in tha catalyst of the invention (II) include, specifically, chromium, zinc, gold, nickel, ruthenium and the like, but there is no restriction to these. As preferred group (c) elements from the standpoint of catalyst performance and practicality there may be mentionad zinc, gold and chromium.

The catalyst for production of acetic acid according to the invention (II) is a binary catalyst containing (a) -metallic palladium and a group (c) element. Although the structure of the catalyst has not been fully elucidated, the palladium is metallic palladium and the group (c) element is in the form of a metal, a compound or an alloy with metallic palladium, and when these are combined they are believed to exist very close together. The (a) metallic palladium and the group (c) element therefore intera.t expressing very high activity and selectivity,

N :

,« and exhibiting very low carbon dioxide selectivity with excellent acetic acid production activity and selectivity, compared to prior art catalysts.

The compositional ratio of the (a) metallic palladium and the one or more group (c) elements in the catalyst of the invention (II) is preferably (a) 1 gram: (c) 0.005 to 10 grams, and more preferably (a) 1 gram: (c) 0.01 to 5 grams. ’ The loading amount of the (a) metallic palladium with respect to the carrier is the same as for the - catalyst of the invention (I).

The loading amount of the group (c) element with respect to the carrier will differ depending on the particle size and pore structure of the carrier, but it is preferably in the range of 0.0001-3 wt%, and more preferably in the range of 0.001-2 wt, with respect to the carrier. Here, "wt3%" with respect to the carrier refers to the value of the weight of the group (c) element divided by the weight of the carrier. - The amount of the components in the catalyst according to the invention (II) can be measured by the same method as for the catalyst of the invention (I).

A catalyst for production of acetic acid according to the invention (III) will now be explained. The catalyst of the invention (III) is a catalyst for production of acetic acid which is a catalyst used in a process for production of acetic acid by reaction of ethanol and oxygen that comprises (a) metallic palladium, (b) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and

Group 16 elements of the Periodic Table and (c) at least one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group ° elements, Group 10 elements, Group 11 elements and Group 12 elements of the Periodic Table, held on a carrier.

The (a) metallic palladium in the catalyst of the invention (III) is the same as for the catalyst of the invention (I).

Also, in the catalyst of the invention (III), the (b) Group 14 elements, Group 15 elements and Group 16 ] elements of the Periodic Table are the suze as for the catalyst of the invention (I), and the (c) Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elements of the Periodic Table are the same as for the catalyst of the invention (II). The carrier is also the same as for the catalyst of the invention (II).

The catalyst for production of acetic acid according to the invention (III) is a ternary catalyst containing (a) metallic palladium, a group (b) element and a group (c) element. Although the structure of the catalyst has not been fully elucidated, the palladium is metallic palladium, and the group (b) element and the group (c) element are each in the form of a metal, a compound or an alloy with metallic palladium, and when these are combined they are believed.to exist very close together.

The (a) metallic palladium, the group (b) element and the group (c) element therefore interact expressing very high activity and selectivity, and exhibiting very low carbon dioxide selectivity with excellent acetic acid production activity and selectivity, compared to prior art catalysts. -

The compositional ratio of the (a) metallic palladium, the one or more group (b) elements and the one or more group (Cc) elements in the catalyst of the invention (III) is preferably (a) 1 gram:(b) 0.005-10 30 .grams:(c) 0.005 to 10 grams, and more preferably (a) 1 gram: (b) 0.01-5.0 grams: (c) 0.01 to 5 grams.

The loading amount of the (a) metallic palladium and the loading amount of the group (b) element with respect to the carrier are the same as for the catalyst of the invention (I), and the loading amount of the group (c) element is the same as for the catalyst of the invention (II). . wt :

. - The amount of the components in the catalyst according to the invention (III) can be measured by the © same method as for the catalyst of the invention (I).

The process of the invention (IV) will now be explained. The process of the invention (IV) is a process for production of a catalyst for production of acetic acid according to the invention (I), (II) or (III).

The catalyst for production of acetic acid according to the invention (I) can be produced by the following : production process (1) or (2).

Production process (1) for a catalyst for production of acetic acid according to the invention (I) comprises "the following steps 1 and 2. ‘ . © step 1 :

A step wherein the (a) metallic palladium is loaded © on a carrier to obtain a metallic palladium-loaded © catalyst. © Step 2

A step wherein (b) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table is loaded on the metallic palladium-loaded catalyst obtained in step 1 to obtain a catalyst for production of acetic acid.

Production process (2) for a catalyst for production of acetic acid according to the invention (I) comprises the following steps 1 and 2.

Step 1

A step wherein a palladium compound and (b) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table are loaded on a carrier to obtain a palladium compound-loaded catalyst.

Step 2

A step wherein the palladium compound-loaded catalyst obtained in step 1 is reduced to obtain a :

catalyst for production of acetic acid.

In step 1 of production process (1) for a catal yst for production of acetic acid according to the inven tion ; (I), che palladium compound serving as the starti J } material for the metallic palladium is not particula rly restricted. In most cases it is possible to use compounds that can be converted to palladium metal, for example, halides such as palladium chloride, organic acid salts such as palladium acetate, and also palladium nitrate, palladium oxide, palladium sulfate and sodi um . tetrachloropalladate, as well as palladium metal its elf.

There are no particular restrictions on the met hod of loading the metallic palladium or the palladium compound that can be converted to metallic palladiuma on the carrier, and it may be loaded by any method. Foer example, when loading a palladium compound that can be converted to metallic palladium, the palladium composund may be dissolved or suspended in an appropriate solveent such as water or acetone, in an inorganic acid or or—ganic acid such as hydrochloric acid, nitric acid, acetic acid, or the like, or a solution thereof, and then loaded onto the carrier and dried, as the method of loading ontco the carrier.

As loading means there may be mentioned the impregnation method, evaporation to dry hardness met=hod, kneading method and spray method, but there is no limitation to these, vhen loading a palladium compound that can be converted to metallic palladium, there are no particcular restrictions on the method of subsequently convertimg the palladium compound to metallic palladium, i.e. the method of reduction treatment. The reduction treatment may= be carried out in either a liquid phase or vapor phase state, with no particular restrictions so long as time : 35 conc .:ions are common reducing conditions. "iguid phase reduction treatment is usually car—ried out &. room temperature, but it may also be conducte=d ot

- 14 = : a= : with heating to a higher temperature of, specifically, - about 30-50°C. Vapor phase reduction treatment is preferably carried out with heating of the palladium compound-loaded carrier to about 100-600°C in order to achieve total conversion to palladium metal.

Specifically there may be mentioned a method whereby the palladium compound is reduced to metallic palladium - by hydrazine, formalin, hydrogen, methanol, ethylene or

Co the like, either directly or after treatment with an aqueous solution of sodium hydroxide, potassium ) hydroxide, barium hydroxide, sodium metasilicate, etc. to convert the palladium compound to an oxide, hydroxide, or — the like.

The procedure for conversion of ‘the palladium compound that can be converted to metallic palladium into metallic palladium may be carried out after separating the catalyst carrying the palladium compound, or it may ~~ be carried out immediately following the loading procedure. If conditions permit, it is preferably carried out immediately following the loading procedure, without separation. If necessary, the metallic palladium-loaded catalyst may be filtered by a common method and then washed and dried to remove any reaction- inhibiting substances for the catalytic reaction, such as halides or alkali salts of sodium, etc.

The metallic palladium-loaded catalyst can be obtained in the manner described above.

Step 2 of production process (1) for a catalyst for production of acetic acid according to the invention (I) is a step wherein (b) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table is loaded on the metallic palladium-loaded catalyst obtained in step 1 to obtain a catalyst for production of acetic acid.

The starting material of the (b) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the

Periodic Table is not particularly restricted, and it may be the element itself or a halide, nitrate, acetate,

B ph.sphate, sulfate or oxide containing the element, or even a complex with an organic molecule such as acetylacetonato or nitrile as the ligand.

Specifically there may be mentioned chlorides such as selenium chloride, tellurium chloride, antimony chloride, tin chloride, bismuth chloride, lead chloride, etc.; nitrates such as antimony nitrate, tin nitrate, ] bismuth nitrate, lead nitrate, etc.; acetates such as tin acetate, bismuth acetate, lead acetate, etc.; and selenium oxide, selenic acid (H,Se0,) and its salts, selenious acid (H,Se0;) and its salts, metallic selenium, tellurium oxide, telluric acid (HTeO,) and its salts, tellurous acid (H,TeO,) and its salts, metallic tellurium" and the like, but there is no limitation to these.

There are no particular restrictions on the method of loading the starting ma*erial for the group (b) element on the carrier, and it may be loaded by any method. For example, the starting material for the group (b) element may be dissolved or suspended in an appropriate solvent such as water or acetone, or in an inorganic acid or organic acid such as hydrochloric acid, nitric acid, acetic acid, or the like and then impregnated into the carrier and dried, as the method of loading onto the carrier.

As loading means there may be mentioned the impregnation method, evaporation to dry hardness method, kneading method and spray method, but there is no limitation to these.

A catalyst for production of acetic acid according to the invention (I) can be obtained in the manner described above.

Step 1 of production process (2) for a catalyst for prod “tion of acetic acid according to the inventinn (I) is a step wherein a palladium compound and (b) at least . - :

Claims

: CLAIMS E }

1. A catalyst for production of acetic acid by ” . reaction of ethanol and oxygen, comprising (a) palladium

-. and (b) at least one element selected from the group x

+z. consisting of Group 14 elements, Group 15 elements and . Group 16 elements of the Periodic Table, held on a carrier. : . 2. A catalyst for production of acetic acid by i reaction of ethanol and oxygen, comprising (a) palladium ) and (c) at least one element selected from the group ) consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 :;; elements and Group 12 elements of the Periodic Table, .» held on a carrier. you 3. A catalyst for production of acetic acid by =: reaction of ethanol. and oxygen, comprising (a) palladium, (b) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and ~ Group 16 elements of the Periodic Table and (c) at least 0 one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group ll elements and Group 12 elements of the Periodic Table, held on a carrier.

4. A catalyst according to any one of claims 1 to 3, wherein the (a) palladium is metallic palladium.

5. A catalyst according to any one of claims 1 to 4, wherein the carrier is silica.

6. A catalyst according to claim 1, 3 or 5, wherein the (b) at least one element selected from the 0 group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table is selected from selenium, tellurium, antimony, bismuth, tin and lead.

7. A catalyst according to any one of claims 2 to 5 6, wherein the (c) at least one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements,

: . - 85 - Co Group 11 elements and Group 12 elements of the Periodic Table is selected from chromium, gold, manganese and ’ zinc.

8. A process for production of a catalyst for production of acetic acid according to claim 1, which comprises the following steps 1 and 2. Step 1 _ A step wherein (a) metallic palladium is loaded on a carrier to obtain a metallic palladium-loaded catalyst. ) Step 2 A step wherein (b) at least one element selected from the group consisting of Group 14 elements, Grovn 15 elements and Group 16 elements of the Periodic Table is loaded on the metallic palladium-loaded catalyst obtained in step 1 .to obtain a catalyst for production of acetic acid. -

9. A process for production of a catalyst for production of acetic acid accordiag to claim 3, which comprises the following steps 1 and 2. Step 1 A step wherein (a) a palladium compound, (b) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table and (c) at least one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Grcup 12 elements of the Periodic Table are loaded on a carrier to cbtain a palladium compound-loaded catalyst. Step 2 A step wherein the palladium compound-loaded catzlyst obtained in step 1 is reduced to obtain a catalyst for production of acetic acid.

10. A process for production of a catalyst for production of acetic acid according to claim 3, w-ich comprises the following steps 1 to 3.

- 86 - Coe g - Step.1 CE Co EN : A step wherein (a) a palladium compound and (c) : at least one element selected from the group consisting

> ~.. of Group 6 elements, Group 7 elements, Group 8 elements,

_.:- Group 9 elements, Group 10 elements, Group 11 elements “ “t.. and Group 12 elements of the Periodic Table are loaded on . 7. a carrier to obtain a palladium compound-loaded catalyst. oe NS Step 2 : ag A step wherein the palladium compound-loaded catalyst obtained in step 1 is reduced to obtain a ) : metallic palladium-loaded catalyst. . Step 3 - SE A step wherein (b) at least one element : x: selected from the group consisting of Group 14 elements, . 15 wg. Group 15 elements and Group 16 elements of the Periodic . +. Table is loaded on the metallic palladium-loaded catalyst g +: obtained in step 2 to obtain a catalyst for production of : » acetic acid. i

11. A process for production of acetic acid, ; 20 comprising reacting ethanol and oxygen in the presence of a catalyst for production of acetic acid according to any one of claims 1 to 7.

12. A process according to claim 11, wherein ethanol and oxygen are reacted in the presence of water.

13. A process according to claim 11 or 12, wherein ethanol and oxygen are reacted in a liquid phase.

14. A process according to claim 11 or 12, wherein ethanol and oxygen are reacted in a vapor phase.

15. A process according to claim 14, wherein the concentration of water in the starting gas is 0.1 to 50% by volume. : 16. A process according to any one of claims 11 to . 13, wherein the starting gas or liquid is blended with acetaldehyde and/or diethyl ether and then the reaction is effected. a 17. A catalyst for production of acetic acid and w ethyl acetate by reaction of ethanol and oxygen,

i - 87 - comprising (a).palladium and (b) at least one compoun. d* _ selected from the group consisting of inorganic acids and salts thereof.

l€. A catalyst for production of acetic acid an d ethyl acetate by reaction of ethanol and oxygen, comprising (a) palladium, (b) at least one compound selected from the group consisting of inorganic acids and : salts thereof and (c) at least one element selected f rom the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table. :

19. A catalyst for production of acetic acid an.d ethyl acetate by reaction of ethanol and oxygen, comprising (a) palladium, (b) at least one compound selected from the group consisting of inorganic. acids. and salts thereof and (d) at least one element selected f rom the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 1.0 elements, Group 11 elements and Group 12 elements of the Periodic Table. J

20. A catalyst for production of acetic acid ammd ethyl acetate by reaction of ethanol and oxygen, comprising (a) palladium, (b) at least one compound selected from the group consisting of inorganic acidss and salts thereof, (c) at least one element selected from the group consisting of Group 14 elements, Group 15 eleme=nts and Group 16 elements of the Periodic Table and (d) aat least one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elements of the Periodic Table.

21. A catalyst according to any one of claims M7 to 20, wherein the (a) palladium is metallic palladium.

22. A catalyst according to any one of claims ®7 to 21, wherein the (b) at least one compound selected fr—om the group consisting of inorganic acids and salts thereof is selected from phosphoric acid and salts thereof, =nd heteropoly acids and salts thereof.

: © 23. A catalyst according to-any one of claims 17 ‘to 22, wherein the (b) at least one compound selected from ” F -- the group consisting of inorganic acids and salts thereof B ol 4: 1s selected from heteropoly acids and salts thereof and B = <> the heteropoly acids are selected from tungstosilicic

: . ~ acid, tungstophosphoric acid, molybdosilicic acid, molybdophosphoric acid, vanadotungstosilicic acid, To ~% vanadotungstophosphoric acid, vanadomolybdosilicic acid : Co #¥. and vanadomolybdophosphoric acid. : 10 24. A catalyst according te any one of claims 18

~. and 20 to 23, wherein the (c) at least one element - selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic - *¥ Table is selected from selenium, tellurium, antimony, : 15 +z. bismuth and lead. * aE 25. A catalyst according to any one of claims 19 to E + 24, wherein the (d) at least one element selected from - the group consisting ot Group 6 elements, Group 7 : * elements, Group 8 elements, Group 9 elements, Group 10 i 20 ~~ elements, Group 11 elements and Group 12 elements of the Periodic Table is selected from chromium, gold, manganese : and zinc.

26. A catalyst according to any one of claims 17 to 25, wherein the catalyst components are held on a carrier.

27. A catalyst according to claim 26, wherein the carrier is silica.

28. A process for production of a catalyst for production of acetic acid and ethyl acetate according to c= claim 17, which comprises the following steps 1 and 2. Step 1 N A step wherein (a) metallic palladium is loaded ; on a carrier toc obtain a metallic palladium-loaded catalyst. 3% } Step 2 a A step wherein (b) at least one compound “ selected from the group consisting of inorganic acids and

, _ 89 - a salts thereof is loaded on the metallic palladium-loadéd catalyst obtained in step 1 to obtain a catalyst for ¥ production of acetic acid and ethyl acetate.

29. A process for production of a catalyst for production of acetic acid and ethyl acetate according to claim 18, which comprises the following steps 1 and 2. Step 1 A step wherein (a) metallic palladium and (c) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 - elements of the Periodic Table are loaded on a carrier to obtain a metallic palladium-loaded catalyst. ) Step 2 A step wherein (b) at least one compound selected from the group consisting of inorganic acids and salts thereof is loaded on the metallic palladium-loaded catalyst obtained in step 1 to obtain a catalyst for. production of acetic acid and ethyl acetate.

30. A process for production of a catalyst for production of acetic acid and ethyl acetate according to claim 18, which comprises the following steps 1 and 2. Step 1 A step wherein (a) metallic palladium is loaded on a carrier to obtain a metallic palladium-loaded catalyst. Step 2 A step wherein (b) at least one compound selected from the group consisting of inorganic acids and salts thereof and (c) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table are loaded on the metallic palladium-loaded catalyst obtained in step 1 to obtain a catalyst for production of acetic acid and ethyl acetate.

31. A process for production of a catalyst for production of acetic acid and ethyl acetate accc -ding to claim 19, which comprises the following steps 1 and 2.

- 90 - oo ) ’ . Step.1-. EN Co ES } A step wherein (a) metallic palladium and (d) - : £ ~ at least one element selected from the group consisting # “of Group 6 elements, Group 7 elements, Group 8 elements, w 5h Group 9 elements, Group 10 elements, Group 11 elements CF “. and Group 12 elements of the Periodic Table are loaded on a carrier to obtain a metallic palladium-loaded catalyst. E gS Step 2 A step wherein (b) at least one compound N 10 selected from the group consisting of inorganic acids and 2 salts thereof is loaded on the metallic palladium-loaded -- catalyst obtained in step 1 to obtain a catalyst for E ~~ production of acetic acid and ethyl acetate. = “i 32. A process for production of a catalyst for : 15 «= production of acetic acid and ethyl acetate according to claim 19, which comprises the following steps 1 and 2. i i Step 1 ) - ; A step wherein (a) metallic palladium 1s loaded on a carrier to obtain a metallic palladium-loaded catalyst. Co Step 2 A step wherein (b) at least one compound selected from the group consisting of inorganic acids and salts thereof and (d) at least one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elements of the To Periodic Table are loaded on the metallic palladium- : loaded catalyst obtained in step 1 to obtain a catalyst : 30 for production of acetic acid and ethyl acetate.

33. A process for production of a catalyst for production of acetic acid and ethyl acetate according to . claim 20, which comprises the following steps 1 and 2. g Step 1 ~~ 35 A step wherein (a) metallic palladium, (¢) at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16

. . - 91 - ao elements of the Periodic Table and (d) at least one << element selected from the group consisting of Group 6 k elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Croup 12 elements of the Periodic Table are loaded on a carrier to obtain a metallic palladium~loaded catalyst. Step 2 A step wherein (b) at least one compound selected from the group consisting of inorganic acicis and salts thereof is loaded on the metallic palladium-lcaded. catalyst obtained in step 1 to obtain a catalyst foxx production of acetic acid and ethyl acetate. : 34. A process for production of a catalyst fox production of acetic acid and ethyl acetate accordimg to claim 20, which comprises the following steps 1 and 2. . Step 1 A step wherein (a) metallic palladium is loaded on a carrier to obtain a metallic palladium-loaded catalyst. ) Step 2 A step wherein (b) at least one compound selected from the group consisting of inorganic acieds and salts thereof, (c) at least one element selected freom the group consisting of Group 14 elements, Group 15 elemnents and Group 16 elements of the Periodic Table and (d) at least one element selected from the group consistine«g of Group 6 elements, Group 7 elements, Group 8 element s, Group 9 elements, Group 10 elements, Group ll elememts and Group 12 elements of the Periodic Table are loa-ded on the metallic palladium-loaded catalyst obtained in step 1 to obtain a catalyst for production of acetic acid and ethyl acetate.

35. BA process for production of a catalyst fo x production of acetic acid and ethyl acetate accordi ng to claim 20, which comprises the following steps 1 and 2. Step 1 A step wherein (a) metallic palladium and (d)

W/O 00/61535 : PCT/JP00/02203 - 92 EIS - at least one element selected from the group consisting: of Group 6 elements, Group 7 elements, Group 8 elements, - ES : Group 9 elements, Group 10 elements, Group 11 elements : s .-. and Group 12 elements of the Periodic Table are loaded on —:z a carrier to obtain a metallic palladium-loaded catalyst.

. Step 2 mT Ce so : : A step wherein (b) at least one compound

..:. Selected from the group consisting of inorganic acids and ~ —:; Salts thereof and (c) at least one element selected from the group consisting of Group 14 elements, Group 15 - ; elements and Group 16 elements of the Periodic Table are o loaded on the metallic palladium-loaded catalyst obtained

. —.. in step 1 to obtain a catalyst for production of acetic ; acid and ethyl acetate.

_... 36. A process for production of a catalyst for i -,. production of acetig¢ acid and ethyl acetate according to a -- claim 290, which comprises the following steps 1 and 2. B - Step 1 : E Lo A step wherein (a) metallic palladium and (c) : 20 at least one element selected from the group consisting of Group 14 elements, Group 15 elements and Group 16 elements of the Periodic Table are loaded on a carrier to obtain a metallic palladium-loaded catalyst. Step 2 A step wherein (b) at least one compound selected from the group consisting of inorganic acids and salts thereof and (d) at least one element selected from the group consisting of Group 6 elements, Group 7 elements, Group 8 elements, Group 9 elements, Group 10 elements, Group 11 elements and Group 12 elements of the Periodic Table are loaded on the metallic palladium- loaded catalyst obtained in step 1 to obtain a catalyst for production of acetic acid and ethyl acetate.

37. A process for production of acetic acid and ethyl acetate, comprising reacting ethanol and oxygen in the presence of a catalyst for production of acetic acid and ethyl acetate according to any one of claims 17 to

38. A process according to claim 37, wherein the hs etharol and oxygen are reacted in the prasence of water.

39. A process according to claim 37 or 38, wherein Ss the ethanol and oxygen are reacted in a liquid phase.

40. A process according to claim 37 or 38, wherein the ethanol and oxygen are reacted in a vapor phase. : 41. A process according to claim 40, wherein the concentration of water in the starting gas is 0.1 to 50% by volume. .

42. A process according to any one of claims 37 to 41, wherein the starting gas or liquid is blended with acetaldehyde and/or diethyl ether and/or ethylene and then the reaction is effected.

15. 43. A process according to any one of claims 37 to 41, wherein the starting gas or liquid is blended with acetic acid and then the reaction is effected.

44. A process according to claim 43, wherein after obtaining acetic acid and ethyle acetate by reacting ethanol and oxygen, ethyl acetate is separated from the reaction mixture to be collected, while acetic acid is returned to the reaction system to be reacted.

PCT/JP00/02203

45. A catalyst for production of acetic acid including any new and inventive integer or combination thereof herein described.

46. A process for production of a catalyst for production of acetic acid including any new and inventive integer or combination thereof herein described.

47. A process for production of acetic acid including any new and inventive integer or combination thereof herein described.

48. A catalyst for production of acetic acid and ethyl acetate by reaction of ethanol and oxygen including any new and inventive integer or combination thereof herein described.

49. A process for production of a catalyst for production of acetic acid and ethyl acetate including any new and inventive integer or combination thereof herein described. AMENDMENT DATED THIS 29TH DAY OF NOVEMBER 2001-11-29 JOHN & KERNICK FOR THE APPLICANT