Preparation of high-quality oxo process alcohols from inconstant raw material sources

Patent metadata

Field	Value
Publication number	US-9914681-B2
Application number	US-201514717183-A
Country	US
Kind code	B2
Filing date	May 20, 2015
Priority date	May 20, 2014
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

Abstract

The preparation of high-quality oxo process alcohols from inconstant raw material sources is the technically demanding problem which is addressed by a process for continuously preparing an alcohol mixture, in which an input mixture which contains an olefin and has a composition that changes over time is subjected to an oligomerization to obtain an oligomerizate and at least a portion of the olefin oligomers present in the oligomerizate are hydroformylated with carbon monoxide and hydrogen in a hydroformylation in the presence of a homogeneous catalyst system to give aldehydes, at least some of which are converted to the alcohol mixture by subsequent hydrogenation. The process provides a constant plasticizer quality to be produced over a long production period and, optionally, a higher throughput with the same product quality. This is achieved a) by control of the temperature and/or the conversion of the oligomerization as a function of the current composition of the oligomerizate; and b) by control of the composition of the catalyst system and/or of the pressure of the hydroformylation as a function of the current composition of the aldehydes.

First claim

The invention claimed is:

1. A process for continuously preparing an alcohol mixture, said process comprising:
oligomerizing an input mixture, which comprises an olefin and has a composition that changes over time, to obtain an oligomerizate comprising olefin oligomers;
hydroformylating at least a portion of the olefin oligomers present in the oligomerizate with carbon monoxide and hydrogen in the presence of a homogeneous catalyst system comprising rhodium and at least two different monophosphite ligands to give aldehydes; and
subsequently hydrogenating at least a portion of the aldehydes to obtain said alcohol mixture;
wherein
a composition of the oligomerizate and a composition of the aldehydes are determined during said process,
a temperature and/or a conversion in the oligomerization are controlled as a function of a current composition of the oligomerizate, and
a composition of the catalyst system during the hydroformylating is controlled by metered addition of one of the at least two monophosphite ligands into the hydroformylation as a function of a current composition of the aldehydes.

2. The process according to claim 1 , wherein the composition of the oligomerizate and the composition of the aldehydes are determined continuously, and the oligomerizing and/or the hydroformylating are controlled continuously.

3. The process according to claim 1 , wherein at least the hydroformylating is controlled in such a way that a first scalar controlled variable calculated from the composition of the aldehydes is kept constant.

4. The process according to claim 3 , wherein the oligomerizing is controlled in such a way that the first scalar controlled variable calculated from the composition of the aldehydes is kept constant.

5. The process according to claim 3 , wherein the first scalar controlled variable is an approximation of the viscosity of an ester mixture obtained by esterification of the alcohol mixture or by transesterification with the aid of the alcohol mixture.

6. The process according to claim 1 , wherein the oligomerizing is controlled in such a way that a second scalar controlled variable calculated from the composition of the olefin oligomers is kept constant.

7. The process according to claim 6 , wherein the second scalar controlled variable is an approximation of the iso index of the oligomerizate.

8. The process according to claim 1 , wherein the input mixture comprises an olefin having four carbon atoms which is oligomerized in the course of the oligomerization to give olefin oligomers having eight, twelve and sixteen carbon atoms, and the olefin oligomers having eight carbon atoms are removed from the oligomerizate and hydroformylated to aldehydes having nine carbon atoms.

9. The process according to claim 8 , wherein the input mixture comprises a combination of the following compound mass flow rates which vary within the specified compound mass flow rate ranges with a respective rate of variation within the specified range of rates of variation:

compound
compound 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 .

10. The process according to claim 1 , wherein the oligomerizing is effected in the presence of a heterogeneous nickel catalyst.

11. The process according to claim 1 , wherein the oligomerization is operated in circulation mode, in such a way that a proportion of the oligomerizate drawn off from the oligomerization is recycled into the oligomerization,
wherein
a conversion of said input mixture in the oligomerization is controlled by varying the proportion of an oligomerizate recycled.

12. The process according to claim 1 , wherein the one monophosphite ligand is metered in such a way that the molar ratio of the sum total of all the monophosphite ligands to rhodium remains constant, taking account of ligand losses.

13. The process according to claim 1 , wherein the homogeneous catalyst system comprises exactly two different monophosphite ligands, the first monophosphite ligand being a compound of structural formula II, and
wherein the second monophosphite ligand is a compound of structural formula Ia, Ib or III:

wherein, in Ia,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from the group consisting of:
—H, —(C 1 -C 12 alkyl), —O—(C 1 -C 12 alkyl), —O—(C 6 -C 20 aryl), —(C 6 -C 20 aryl), halogen, —COO—(C 1 -C 12 alkyl), —CONH—(C 1 -C 12 alkyl), —(C 6 -C 20 aryl)-CON[(C 1 -C 12 alkyl)] 2 , —CO—(C 1 -C 12 alkyl), —CO—(C 6 -C 20 aryl), —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , and —N[(C 1 -C 12 alkyl)] 2 ; and
R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from the group consisting of:
—H, —(C 1 -C 12 alkyl), —O—(C 1 -C 12 alkyl), —O—(C 6 -C 20 aryl), —(C 6 -C 20 aryl), halogen, —COO—(C 1 -C 12 alkyl), —CONH—(C 1 -C 12 alkyl), —(C 6 -C 20 aryl)-CON[(C 1 -C 12 alkyl)] 2 , —CO—(C 1 -C 12 alkyl), —CO—(C 6 -C 20 aryl), —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , and —N[(C 1 -C 12 alkyl)] 2

wherein, in Ib,
R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from the group consisting of:
—H, —(C 1 -C 12 alkyl), —O—(C 1 -C 12 alkyl), —O—(C 6 -C 20 aryl), —(C 6 -C 20 aryl), halogen, —COO—(C 1 -C 12 alkyl), —CONH—(C 1 -C 12 alkyl), —(C 6 -C 20 aryl)-CON[(C 1 -C 12 alkyl)] 2 , —CO—(C 1 -C 12 alkyl), —CO—(C 6 -C 20 aryl), —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , and —N[(C 1 -C 12 alkyl)] 2

wherein, in II,
R 21 ″, R 22 ″, R 23 ″, R 24 ″, R 25 ″, R 31 ″, R 32 ″, R 33 ″, R 34 ″, R 35 ″, R 41 ″, R 42 ″, R 43 ″, R 44 ″, R 45 ″ are each independently selected from the group consisting of:
—H, —(C 1 -C 12 alkyl), —O—(C 1 -C 12 alkyl), —O—(C 6 -C 20 aryl), —(C 6 -C 20 aryl), halogen, —COO—(C 1 -C 12 alkyl), —CONH—(C 1 -C 12 alkyl), —(C 6 -C 20 aryl)-CON[(C 1 -C 12 alkyl)] 2 , —CO—(C 1 -C 12 alkyl), —CO—(C 6 -C 20 aryl), —COO

Assignees

• Geilen Frank
• Dyballa Katrin Marie
• Hess Dieter
• Peitz Stephan
• Franke Robert
• Fridag Dirk
• Maschmeyer Dietrich
• Reeker Helene
• Stochniol Guido
• Evonik Degussa Gmbh

Inventors

• Geilen Frank
• Dyballa Katrin Marie
• Hess Dieter
• Peitz Stephan
• Franke Robert
• Fridag Dirk
• Maschmeyer Dietrich
• Reeker Helene
• Stochniol Guido

Classifications

• C07C29/141 Primary

  with hydrogen or hydrogen-containing gases · CPC title

• C07C29/14 Primary

  of a —CHO group · CPC title

• C07C45/50

  by oxo-reactions · CPC title

• C07C2/24 Primary

  with metals · CPC title

• C07C67/08

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