Method for ring hydrogenation of dialkyl terephthalates with low by-product formation

Patent metadata

Field	Value
Publication number	US-12565469-B2
Application number	US-202217931559-A
Country	US
Kind code	B2
Filing date	Sep 13, 2022
Priority date	Sep 14, 2021
Publication date	Mar 3, 2026
Grant date	Mar 3, 2026

Abstract

A process for ring hydrogenation of dialkyl terephthalates having C 3 - to C 16 -alkyl groups can be performed in a hydrogenation unit composed of two reaction units in series. In the process, a suitable process parameter in relation to the first reaction unit is adjusted so that a certain reaction conversion is achieved.

First claim

The invention claimed is:

1 . A process for ring hydrogenation of a dialkyl terephthalate having C 3 - to C 16 -alkyl groups, to give a 1,4-cyclohexanedicarboxylic ester having corresponding alkyl groups, the process comprising:
contacting the dialkyl terephthalate with a hydrogen-containing gas, in a hydrogenation unit consisting of a first reaction unit and a second reaction unit connected in series, wherein the first reaction unit and the second reaction unit each consist of one reactor or two or more parallel reactors, wherein reactor(s) of the second reaction unit are operated in a straight pass, wherein reactor(s) of the first reaction unit and the reactor(s) of the second reaction unit each independently comprise a heterogeneous hydrogenation catalyst, wherein the dialkyl terephthalate is used as feed to the reactor(s) of the first reaction unit and the reactor(s) of the second reaction unit, wherein a reaction conversion in the first reaction unit is monitored, and wherein at least one parameter in relation to the first reaction unit, selected from the group consisting of an amount of feed supplied to the first reaction unit (total amount of fresh feed and recycle), an amount of dialkyl terephthalate to be hydrogenated, a reactor temperature in the reactor(s) of the first reaction unit, a temperature increase, a circulation volume flow, a feed/recycle ratio, a ratio of hydrogen to the dialkyl terephthalate, a reactor pressure, a feed composition, an amount of the heterogeneous hydrogenation catalyst, a catalyst composition, if cooling is present, an amount of coolant circulated or an amount of product in a discharge of the first reaction unit, and a combination thereof, is controlled such that a reaction conversion in the range of 85 to 93% is achieved.

2 . The process according to claim 1 , wherein a reactor present in the first reaction unit is operated in a closed loop.

3 . The process according to claim 1 , wherein an amount of by-products in a ring hydrogenation process product after the hydrogenation unit is less than 1.3% by weight.

4 . The process according to claim 1 , wherein a total conversion in the process, based on the hydrogenation unit, is greater than or equal to 99.7%.

5 . The process according to claim 1 , wherein the dialkyl terephthalate is a dialkyl terephthalate having C 4 - to C 10 -alkyl groups.

6 . The process according to claim 5 , wherein the dialkyl terephthalate is prepared by transesterification of dimethyl terephthalate with an alcohol having 4 to 10 carbon atoms, or by esterification of terephthalic acid with an alcohol having 4 to 10 carbon atoms.

7 . The process according to claim 5 , wherein the dialkyl terephthalate is diethylhexyl terephthalate or diisononyl terephthalate.

8 . The process according to claim 1 , wherein the heterogeneous hydrogenation catalyst of the reactor(s) of the first reaction unit and of the reactor(s) of the second reaction unit each comprise a transition metal on a support material.

9 . The process according to claim 8 , wherein the transition metal is a metal from Group 8 of the Periodic Table of the Elements.

10 . The process according to claim 8 , wherein the support material is selected from the group consisting of activated carbon, silicon carbide, aluminium oxide, silicon dioxide, aluminosilicate, a zeolite, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, and a mixture thereof.

11 . The process according to claim 10 , wherein the support material is titanium dioxide or aluminium oxide.

12 . The process according to claim 8 , wherein a transition metal content in the heterogeneous hydrogenation catalyst is in the range from 0.1% to 10% by weight.

13 . The process according to claim 8 , wherein the heterogenous hydrogenation catalyst of both the reactor(s) of the first reaction unit and the reactor(s) of the second reaction unit have the same composition.

14 . The process according to claim 1 , wherein a hydrogenation temperature in the ring hydrogenation is in the range from 50 to 250° C.

15 . The process according to claim 1 , wherein the ring hydrogenation is carried out in a pressure range of 3 to 300 bar.

16 . The process according to claim 1 , wherein the reaction conversion of the first reaction unit is in a range of 88 to 92%.

17 . The process according to claim 5 , wherein the dialkyl terephthalate is a dialkyl terephthalate having C 5 - to C 9 -alkyl groups.

18 . The process according to claim 5 , wherein the dialkyl terephthalate is a dialkyl terephthalate having C 8 - or C 9 -alkyl groups.

19 . The process according to claim 9 , wherein the transition metal is ruthenium.

20 . The process according to claim 12 , wherein the transition metal content in the heterogeneous hydrogenation catalyst is in a range from 0.5% to 3% by weight.

Assignees

• Evonik Oxeno Gmbh & Co Kg

Inventors

• Zanthoff Horst-Werner
• Bauer Julia
• Grass Michael
• Schneider Thomas

Classifications

• B01J23/462

  Ruthenium · CPC title

• B01J21/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• B01J21/04

  Alumina · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C07C69/82

  Terephthalic acid esters · CPC title