Method for preparing dialkyl carbonate

Patent metadata

Field	Value
Publication number	US-9334228-B2
Application number	US-201314057111-A
Country	US
Kind code	B2
Filing date	Oct 18, 2013
Priority date	Apr 20, 2011
Publication date	May 10, 2016
Grant date	May 10, 2016

Abstract

Disclosed is a method for preparing a dialkyl carbonate, in which a dialkyl carbonate such as dimethyl carbonate is economically prepared in an environmentally-friendly manner at a higher yield while reducing generation of a by-product. The method for preparing the dialkyl carbonate includes reacting urea, an alkyl carbamate having 1 to 3 carbon atoms, or a mixture thereof with a monovalent alcohol having 1 to 3 carbon atoms in the presence of a room temperature ionic liquid and a catalyst including a salt of a transition metal or a rare earth metal.

First claim

What is claimed is:

1. A method for preparing a dialkyl carbonate, comprising:
reacting urea, an alkyl carbamate having 1 to 3 carbon atoms, or a mixture thereof with a monovalent alcohol having 1 to 3 carbon atoms in the presence of a room temperature ionic liquid comprising a cation that is capable of generating a hydrogen ion (H + ) and a hydrophobic anion containing fluorine and a catalyst comprising a salt of a transition metal or a rare earth metal,
wherein the salt of the transition metal or the rare earth metal is a nitrate, a halide or a hydrate of the transition metal or the rare earth metal.

2. The method of claim 1 , wherein the salt of the transition metal comprises a salt of a transition metal of Group III or IV.

3. The method of claim 1 , wherein the catalyst comprises a salt of Zr, Ce, La, or Y.

4. The method of claim 1 , wherein the catalyst comprises ZrO(NO 3 ) 2 , Ce(NO 3 ) 3 , CeCl 3 , ZrCl 4 , La(NO 3 ) 3 , or LaCl 3 , or a hydrate thereof.

5. The method of claim 1 , wherein the cation is a quaternary ammonium-based cation, an imidazolium-based cation, a N-hydroxyalkylpyridium-based cation, a pyrazolium-based cation, a pyrrolinium-based cation, a quaternary phosphonium-based cation, a thiazolium-based cation, or a sulfonium-based cation having an alkyl group or a hydroxyalkyl group, and
the anion is a bis(trifluoromethylsulfonyl)imide anion, a trifluoromethanesulfonate anion, or a tris(trifluoromethylsulfonyl)methanide anion.

6. The method of claim 5 , wherein the room temperature ionic liquid is [Choline] [NTf 2 ].

7. The method of claim 1 , wherein the reaction is carried out at a temperature of 130 to 300° C. and a pressure of 0.1 to 15 atm.

8. The method of claim 1 , wherein the urea, the alkyl carbamate, or the mixture thereof, and the monovalent alcohol, are used at a molar ratio of 1:1 to 1:100.

9. The method of claim 1 , wherein the catalyst and the room temperature ionic liquid are used at a weight ratio of 1:1 to 1:1000.

10. The method of claim 1 , wherein the reaction of the urea, the alkyl carbamate, or the mixture thereof with the monovalent alcohol comprises:
a first reaction of reacting the urea, the alkyl carbamate having 1 to 3 carbon atoms, or the mixture thereof with the monovalent alcohol having 1 to 3 carbon atoms in the presence of the room temperature ionic liquid and the catalyst; and
a second reaction of further reacting a product of the first reaction to convert isocyanic acid included in the product of the first reaction into alkyl carbamate.

11. The method of claim 10 , wherein the first reaction is carried out in a stirred reactor, and the second reaction is carried out in a fixed-bed reactor.

12. The method of claim 11 , wherein the fixed-bed reactor is filled with Raschig rings or a formed body in which a metal oxide catalyst is impregnated.

13. The method of claim 10 , wherein the second reaction is carried out with addition of the catalyst comprising oxides of one or more metals selected from the group consisting of Zr, Ce, Zn, Ti, Pb, and Mg.

14. The method of claim 1 , further comprising
after the reaction of the urea, the alkyl carbamate, or the mixture thereof with the monovalent alcohol,
separating a resultant product of such reaction from a product comprising dialkyl carbonate, a by-product comprising ammonia, and an unreacted residue comprising monovalent alcohol and alkyl carbamate.

15. The method of claim 14 , wherein the unreacted residue comprising monovalent alcohol and alkyl carbamate is circulated into the reaction and reused.

16. The method of claim 1 , further comprising,
after the reaction of the urea,
the alkyl carbamate, or the mixture thereof with the monovalent alcohol,
distilling a resultant product of such reaction in a first distillation column to circulate an unreacted residue of a column bottom into the reaction and purifying a by-product at a column top to form a first product comprising ammonia, monovalent alcohol, and dialkyl carbonate;
distilling the first product in a second distillation column to circulate the unreacted residue of the column bottom into the reaction and form a second product comprising monovalent alcohol and dialkyl carbonate at the column top; and
distilling the second product in a third distillation column to recover a final product including dialkyl carbonate at the column bottom.

17. The method of claim 16 , further comprising
before distilling the second product in the third distillation column,
membrane separating the second product comprising monovalent alcohol and dialkyl carbonate in a membrane separation device to further separate the unreacted residue to circulate the unreacted residue into the second distillation column and form a product including dialkyl carbonate at a concentration that is higher than the concentration of the second product in the secondarily distilling step, and
wherein the first, second, and third distillation columns are atmospheric distillation columns, and the membrane separation device is a pervaporation device.

18. The method of claim 16 , wherein the first and the second distillation columns are atmospheric distillation columns, and the third distillation column is a high pressure distillation column.

Assignees

• Res Inst Ind Science & Tech

Inventors

• Baik Joon Hyun
• Koh Jae Cheon
• Kim Kyong Tae
• Koh Dong Jun
• Sa Young Sam
• Kim Yun Min
• Kim Chul Ung

Classifications

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C68/00 Primary

  Preparation of esters of carbonic or haloformic acids · CPC title

• C07C69/96

  Esters of carbonic or haloformic acids · CPC title