Influencing the viscosity of N-butene-based ester mixtures by controlled use of ethene in the preparation of the ester precursors

Patent metadata

Field	Value
Publication number	US-10000440-B2
Application number	US-201615356507-A
Country	US
Kind code	B2
Filing date	Nov 18, 2016
Priority date	Nov 19, 2015
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

The invention relates to a process for preparing an ester mixture, in which an n-butene-containing feed mixture having a composition which changes over time is first oligomerized and then converted by hydroformylation, hydrogenation and esterification to an ester mixture. In this process, an approximation of the actual viscosity of the ester mixture is determined. The problem that it addresses is that of specifying a comparatively simple process which enables conversion of an n-butene with a variable composition over time to an ester mixture having a viscosity which can be kept very substantially constant over a long period even when an inconstant C 4 source which delivers fluctuating qualities over this period is utilized. This is achieved through controlled use of a second raw material, namely ethene. It has been found that the viscosity of n-butene-based ester mixtures can be influenced by controlled use of ethene in the preparation of the ester precursors. Specifically, the invention proposes two measures by which the ethene can be used: either directly as C 2 olefin or as C 8 olefin after prior separate oligomerization.

First claim

What is claimed is:

1. Process for preparing an ester mixture in which an n-butene-containing feed mixture having a composition which varies over time is subjected to a first oligomerization to obtain an oligomerizate and at least some of the butene oligomers present in the oligomerizate are hydroformylated to aldehydes, of which at least some are hydrogenated by subsequent hydrogenation to an alcohol mixture which is then converted to the ester mixture, and in which an approximation of the actual viscosity of the ester mixture is determined, characterized in that ethene oligomers which are obtained by subjecting an n-butene-free, ethene-containing and hexene-containing feed mixture to a second oligomerization conducted separately from the first oligomerization are added in a controlled manner to the butene oligomers to be hydroformylated, such that the second oligomerization is a co-oligomerization of ethene and hexene.

2. Process according to claim 1 , characterized in that
a) the hexene is sourced from a third oligomerization which is conducted separately from the first and second oligomerizations, in which propene is dimerized, or
b) the hexene is sourced from a third oligomerization which is conducted separately from the first and second oligomerizations, in which ethene is trimerized; or
c) the hexene is sourced from the second oligomerization.

3. Process according to claim 1 , characterized in that the second oligomerization is effected in the presence of a liquid inert solvent in which the ethene is at least partly dissolved and which is separated from the ethene oligomers after the second oligomerization has been conducted.

4. Process according to claim 1 , characterized in that the controlled addition of the ethene oligomers to the butene oligomers to be hydroformylated is effected in such a way that a target viscosity of the ester mixture is first fixed, the approximation of the actual viscosity of the ester mixture determined is compared with the target viscosity of the ester mixture, and the amount of the ethene oligomers added to the butene oligomers to be hydroformylated is increased if the approximation of the actual viscosity is greater than the target viscosity, or the amount of the ethene oligomers added to the butene oligomers to be hydroformylated is reduced if the approximation of the actual viscosity is less than the target viscosity.

5. Process according to claim 1 , characterized in that the approximation of the actual viscosity of the ester mixture is determined by measuring the viscosity of the ester mixture.

6. Process according to claim 1 , characterized in that the approximation of the actual viscosity of the ester mixture is determined by calculation, the calculation being based on analysis of the alcohol mixture, on an analysis of the aldehydes to be hydrogenated, or on an analysis of the oligomers to be hydroformylated.

7. Process according claim 1 , characterized in that the n-butene-containing feed mixture is composed of a combination of the following substance mass flow rates which vary within the specified substance mass flow rate ranges with a respective rate of variation within the specified range of rates of variation:

Substance
Substance mass flow rate
Rate of variation

Isobutene:
0 kg/s to 1 kg/s
−0.05 g/s 2 to 0.05 g/s 2

1-Butene:
0 kg/s to 6 kg/s
−0.30 g/s 2 to 0.30 g/s 2

2-Butene (cis + trans):
 1 kg/s to 13 kg/s
−0.30 g/s 2 to 0.30 g/s 2

Isobutane:
0 kg/s to 3 kg/s
−0.15 g/s 2 to 0.15 g/s 2

n-Butane:
1 kg/s to 7 kg/s
−0.30 g/s 2 to 0.30 g/s 2

Other materials:
0 kg/s to 1 kg/s
−0.05 g/s 2 to 0.05 g/s 2 .

8. Process according to claim 1 , characterized in that the first oligomerization and/or the second and/or the third oligomerization is effected in the presence of a heterogeneous catalyst containing nickel, silicon and aluminium.

9. Process according to claim 1 , characterized in that the hydroformylation is conducted in the presence of a homogeneous catalyst system comprising
either cobalt or rhodium.

10. Process according to claim 1 , characterized in that the conversion of the alcohol mixture to the ester mixture is effected by esterifying the alcohol mixture with a carboxylic acid or carboxylic anhydride, or by obtaining the ester mixture by means of a transesterification of an existing ester with the alcohol mixture.

11. Process according to claim 10 , characterized in that the alcohol mixture is a mixture of isomeric nonyl alcohols which is reacted with phthalic acid or phthalic anhydride to give diisononyl phthalate.

Assignees

• Evonik Degussa Gmbh

Inventors

• Reeker Helene
• Stochniol Guido
• Maschmeyer Dietrich
• Zanthoff Horst-Werner
• Schallenberg Jörg
• Geilen Frank
• Dyballa Katrin Marie
• Fridag Dirk
• Peitz Stephan
• Altmann Lena
• Franke Robert

Classifications

• C07C2521/12

  Silica and alumina · CPC title

• C07C69/80

  Phthalic acid esters · CPC title

• C07C45/505

  Asymmetric hydroformylation · CPC title

• C07C45/50

  by oxo-reactions · CPC title

• C07C67/08 Primary

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title