Olefin production method

Patent metadata

Field	Value
Publication number	US-9567266-B2
Application number	US-201214372370-A
Country	US
Kind code	B2
Filing date	Dec 20, 2012
Priority date	Jan 20, 2012
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

The invention has objects of providing an olefin production method which can produce an olefin with high efficiency by the dehydration reaction of an alcohol even in the presence of a ketone without the occurrence of side reactions such as the Aldol condensation of the ketone, as well as providing an olefin production method which can produce an olefin with high activity and high selectivity in a single reaction step by directly reacting a corresponding ketone and hydrogen. The former olefin production method of the invention produces an olefin from an alcohol using a silica gel (A) as a dehydration catalyst which is obtained by bringing a silica gel (X) prepared from an alkyl orthosilicate into contact with a water-soluble aluminum compound and calcining the contact product or is obtained from a wet-process silica gel (Y) prepared from an alkali silicate and which contains an aluminum compound at 10 to 1000 ppm in terms of aluminum element as well as an alkali metal and an alkaline earth metal at a total of 0 to 350 ppm. The latter olefin production method produces an olefin from a ketone and hydrogen in a single reaction step in the presence of the silica gel (A) and a silver-containing inorganic substance (B).

First claim

The invention claimed is:

1. An olefin production method, comprising reacting an alcohol of Formula (I) below in a dehydration reaction using a chemically treated silica gel (A) as a dehydration catalyst to thereby produce an olefin represented by Formula (II) below, wherein the silica gel (A) contains 10 to 1000 ppm of aluminum and 0 to 350 ppm of a metal selected from the group consisting of an alkali metal, an alkaline earth metal, and combinations thereof:

in Formulae (I) and (II), R 1 is a group selected from alkyl groups of 1 to 5 carbon atoms and aryl groups of 6 to 12 carbon atoms; and R 2 is an atom or a group selected from a hydrogen atom, alkyl groups of 1 to 5 carbon atoms and aryl groups of 6 to 12 carbon atoms.

2. The olefin production method according to claim 1 , wherein the silica gel (A) is a silica gel (A1) which is obtained by bringing a silica gel (X) prepared from an alkyl orthosilicate into contact with a water-soluble aluminum compound and calcining the contact product and which contains 10 to 1000 ppm of aluminum and 0 to 20 ppm of a metal selected from the group consisting of an alkali metal, an alkaline earth metal, and combinations thereof.

3. The olefin production method according to claim 1 , wherein the silica gel (A) is a silica gel (A2) which is obtained from a wet-process silica gel (Y) prepared from an alkali silicate and which contains 10 to 1000 ppm of aluminum and 1 to 350 ppm of a metal selected from the group consisting of an alkali metal, an alkaline earth metal, and combinations thereof.

4. The olefin production method according to claim 3 , wherein the silica gel (A2) is a silica gel (A2-1) which is obtained by subjecting a wet-process silica gel (Y) prepared from an alkali silicate to a contact treatment with an acidic aqueous solution comprising a pH of 0.5 or greater and less than 7, and calcining the product.

5. The olefin production method according to claim 3 , wherein the silica gel (A2) is a silica gel (A2-2) which is obtained by bringing a wet-process silica gel (Y) prepared from an alkali silicate into contact with a water-soluble aluminum compound, and calcining the contact product.

6. The olefin production method according to claim 3 , wherein the silica gel (A2) is a silica gel (A2-3) which is obtained by subjecting a wet-process silica gel (Y) prepared from an alkali silicate to a contact treatment with an acidic aqueous solution comprising a pH of 0.5 or greater and less than 7, then bringing the product into contact with a water-soluble aluminum compound, and calcining the contact product.

7. The olefin production method according to claim 3 , wherein the silica gel (A2) is a silica gel (A2-4) which is obtained by bringing a wet-process silica gel (Y) prepared from an alkali silicate into contact with a water-soluble aluminum compound, then subjecting the contact product to a contact treatment with an acidic aqueous solution comprising a pH of 0.5 or greater and less than 7, and calcining the product.

8. The olefin production method according to claim 1 , wherein a ketone represented by Formula (III) below is present in an amount in terms of weight that is 0.01 to 10 times the amount of the alcohol represented by Formula (I):

in Formula (III), R 3 is a group selected from alkyl groups of 1 to 5 carbon atoms and aryl groups of 6 to 12 carbon atoms; and R 4 is an atom or a group selected from a hydrogen atom, alkyl groups of 1 to 5 carbon atoms and aryl groups of 6 to 12 carbon atoms.

9. The olefin production method according to claim 8 , wherein R 3 in Formula (III) is an identical group to R 1 in Formulae (I) and (II), and R 4 in Formula (III) is an identical atom or group to R 2 in Formulae (I) and (II).

10. An olefin production method, comprising producing an olefin represented by Formula (II) below from a ketone of Formula (III) below and hydrogen in a single reaction step in the presence of a chemically treated silica gel (A) which contains 10 to 1000 ppm of aluminum and 0 to 350 ppm of a metal selected from the group consisting of an alkali metal, an alkaline earth metal, and combinations thereof, and a silver-containing inorganic substance (B):

in Formula (II), R 1 is a group selected from alkyl groups of 1 to 5 carbon atoms and aryl groups of 6 to 12 carbon atoms; and R 2 is an atom or a group selected from a hydrogen atom, alkyl groups of 1 to 5 carbon atoms and aryl groups of 6 to 12 carbon atoms;
in Formula (III), R 3 is a group selected from alkyl groups of 1 to 5 carbon atoms and aryl groups of 6 to 12 carbon atoms; and R 4 is an atom or a group selected from a hydrogen atom, alkyl groups of 1 to 5 carbon atoms and aryl groups of 6 to 12 carbon atoms; and
R 3 in Formula (III) and R 1 in Formula (II) are the identical groups, and R 4 in Formula (III) and R 2 in Formula (II) are the identical atoms or groups.

11. The olefin production method according to claim 10 , wherein the silver-containing inorganic substance (B) contains at least one Group 13 (IIIA) element in the periodic table.

12. The olefin production method according to claim 8 , wherein the ketone represented by Formula (III) is acetone, and the olefin represented by Formula (II) is propylene.

13. The olefin production method according to claim 10 , wherein the reaction is carried out in the presence of a mixture of the silica gel (A) and the silver-containing inorganic substance (B).

14. The olefin production method according to claim 1 , wherein the reaction is carried out at a temperature between 50 to 500° C.

15. The olefin production method according to claim 10 , wherein the reaction is carried out at a temperature between 50 to 500° C.

Assignees

• Mitsui Chemicals Inc

Inventors

• Ishibashi Masayasu
• Ohkubo Tsuneyuki

Classifications

• C07C2521/12

  Silica and alumina · CPC title

• C07C1/24 Primary

  by elimination of water · CPC title

• C07C2523/04

  Alkali metals · CPC title

• C07C1/20

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title

• C07C2521/08

  Silica · CPC title