EP2867190A1

EP2867190A1 - Method for the production of diisobutene

Info

Publication number: EP2867190A1
Application number: EP13732551.0A
Authority: EP
Inventors: Jens Klabunde; Leif Johnen; Guido D. Frey; Sebastian Geisel; Horst Lange; Heinz Strutz
Original assignee: Oxea GmbH
Current assignee: OQ Chemicals GmbH
Priority date: 2012-07-02
Filing date: 2013-07-01
Publication date: 2015-05-06
Also published as: DE102012105877A1; US20150184202A1; JP2015524384A; TW201406961A; WO2014005978A1; BR112014028816A2; CN104395265A

Abstract

The invention relates to a method for producing diisobutene from enzymatically produced isobutene, the higher purity of which improves the method and the properties of the produced diisobutene.

Description

Process for the preparation of diisobutene

The present invention relates to a process for the preparation of diisobutylene, preferably from renewable raw material sources.

Diisobutene (2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene as main components) is an important industrial chemical as well as an important intermediate in the production of other large industrial compounds. For example, diisobutene is further processed into isononanal, isononanol, isononanoic acid and derivatives of these oxo chemicals extended by one carbon atom (Ullmanns Encyklopadie der technischen Chemie, 4th Edition, 1975, Verlag Chemie, Volume 9, pages 143-145).

Methods for the preparation of diisobutene have been known for some time, and others. in Baerns et. al. Technical Chemistry, 1st edition, Wiley-VCH, Weinheim 2006 described. In most cases, one starts from isobutene obtained from raffinate I, which is acid-catalyzed to diisobutene dimerization. However, due to the immense importance of diisobutene in engineering chemistry, there is a constant search for further improvements in alternative processes and alternative sources of raw materials for the production of diisobutene.

The use of renewable raw materials as starting materials for the production of organic chemicals on an industrial scale is becoming increasingly important. On the one hand, the resources based on crude oil, natural gas and coal are to be spared and on the other hand, renewable resources are used to produce carbon dioxide in a technically usable form

Carbon source bound, which is in principle inexpensive and in large quantities to OD 41643 / SAM: AH Available. Examples of the use of renewable raw materials for the industrial production of organic chemicals include the production of citric acid, 1,3-propanediol, L-lysine, succinic acid, lactic acid and itaconic acid. Renewable resources are not used for the production of diisobutene. Thus, the object is to provide an alternative improved process for the production of diisobutene preferably from renewable raw material sources available. It is of particular importance with regard to the use of the diisobutene that as isomeric isobutene is used as far as possible for the preparation of diisobutene.

This object is achieved by a process for the preparation of diisobutene, comprising the steps: a) fermentative production of isobutene

b) Dimerization of isobutene to diisobutene

c) Purification of the diisobutene

It has surprisingly been found that isobutene produced by fermentation is of such high purity with respect to linear butene isomers that subsequent acid-catalyzed dimerization yields diisobutene in high purity and yield. In the prior art, processes are known in which isobutene is produced biochemically on a laboratory scale in high purity. For example, starting from the direct precursor 3-hydroxyisovalerate (3-hydroxy-3-methylbutyrate), Gogerty, DS and Bobik, TA 2010, Applied and Environmental Microbiology, page 8004-8010 investigated the fermentative-enzymatic synthesis of isobutene GC showed no major amounts of n-butene isomers in the desired product. The by-product carbon dioxide formed in the fermentation and optionally further inerts may optionally be removed in a conventional manner by suitable separation methods. In most embodiments of the invention, the conversion of isobutene to diisobutene can be carried out even without further purification of the isobutene, which is thus a preferred embodiment of the invention. In this embodiment of the invention, the fermentative process according to the invention makes use of the high selectivity to isobutene as C4-01efm. On the other hand, carbon dioxide and other inerts do not interfere with the dimerization of isobutene to diisobutene. In special cases, however, it may prove expedient to first separate carbon dioxide and other inerts from the isobutene.

By "fermentative production" of isobutene is meant, in particular, that isobutene is obtained either by means of microorganisms, preferably from renewable raw materials and / or in a cell-free enzymatic process, also preferably from renewable raw materials.

Isobutene is - as far as is known - not a natural product in the sense that it arises in metabolic processes in organisms in such quantities that an industrial use appears appropriate. However, in very small amounts, isobutene is produced by naturally occurring microorganisms (US4698304, Fukuda, H. 1984 et al, From Agricultural and Biological Chemistry (1984), 48 (6), pp. 1679-82). Thus, in the hitherto known embodiments of the invention, the fermentative production of isobutene by means of modified, non-natural microorganisms or the corresponding modified enzymes. Such microorganisms are known from US2011165644 (AI), which is treated in Example 13, the synthesis of isobutene from glucose in suitable microorganisms. WO2012052427 and WO2011032934 describe further enzymatic reactions which involve the formation of isobutene as a sequence of sequential enzymatic syntheses of

I) acetone to 3-hydroxyisovalerate and

II) 3-hydroxyisovalerate to isobutene and carbon dioxide

describe.

The enzymatically catalyzed breakdown of 3-hydroxyisovalerate to isobutene and carbon dioxide is also addressed in Gogerty, DS and Bobik, TA 2010, Applied and Environmental Microbiology, pages 8004-8010. According to GC, no larger amounts of n-butene isomers were reported in the desired product. Even in aqueous, non-enzymatically catalyzed systems, spontaneous carbon dioxide cleavage from 3-hydroxyisovalerate with the formation of isobutene, which reacts further with the water present in an equilibrium reaction with ter-butanol (Pressman, D. and Lucas, HJ., 1940, Journal of the American Chemical Society, pages 2069-2081). If this sequence of enzymatic syntheses described in I and II is included in a suitable microbial host organism capable of synthesizing acetone from metabolic precursors or transporting externally supplied acetone via the cell wall into the cell interior via passive or active transport, this can not be achieved -natural microorganism Isobutene can be produced with a fermentative process in good yield. Microorganisms that synthesize acetone from various carbohydrates have long been known and are described, inter alia, in Jones, TD and Woods, DR 1986, Microb. Reviews, pages 484 - 524 -. Taylor, DG et al., 1980, Journal of General Microbiology, 118, pages 159-170, are microorganisms describe acetone as the sole source of carbon and are therefore able to transport acetone into the cell via the cell wall.

Another possible metabolic pathway is via the reaction sequence:

I) pyruvate to 2-acetolactate

II) 2-acetolactate to 2,3-dihydroxyisovalerate

III) 2,3-dihydroxyisovalerate to 2-oxoisovalerate

IV) 2-oxoisovalerate to isobutyraldehyde

V) isobutyraldehyde to iso-butanol and

VI) iso-butanol to isobutene and is i.a. in WO2011076689 and WO2011076691. As already described, "diisobutene" is understood to mean 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene as main components and any desired mixtures of these two compounds.

According to a preferred embodiment of the invention, there is no purification of the isobutene between step a) and b), in particular no purification for the removal of linear butene isomers and optionally of inerts such as carbon dioxide and / or nitrogen. The term "purification" is understood to mean in particular (but not limited to) the following processes: - distillation processes (which, however, are made more difficult by the fact that the separation in the

Overall process occurring linear butene isomers requires a lot of effort, since the boiling points of the isomers are very close to each other, see. Kirk-Othmer Encyclopedia of Chemical Technology 3rd Edition 1978, Vol 4, John Wiley & Sons Inc., pp. 358-360).

- Purification or separation process in which isobutene is separated due to the increased chemical reactivity by means of a chemical reaction and then converted back into isobutene. These include u.a. Process, such as reversible proton-catalyzed addition of water to tertiary butanol or the methanol addition to methyl tert-butyl ether (see EP 1489062). Isobutene is then recovered from these addition products by cleavage (see Weissermel, Arpe, Industrielle Organische Chemie, VCH Verlagsgesellschaft, 3.

Edition, 1988, pp. 74-79).

Purification methods in which isobutene, due to the more compact spatial molecular structure, by means of suitable physical size exclusion techniques, e.g. by molecular sieves with a suitable pore size, is separated from linear butene isomers (see WO2012040859, Weissermel, Arpe, Industrial Organic Chemistry, VCH Verlagsgesellschaft, 3rd edition, 1988, p.74).

Purification or separation processes suitable for the removal of carbon dioxide.

According to a preferred embodiment of the invention, the isobutene in step a) is obtained from trisaccharides, disaccharides, monosaccharides, acetone or mixtures thereof. The tri- and disaccharides used are, in particular, raffmose, cellobiose, lactose, isomaltose, maltose and sucrose. The monosaccharides used are, in particular, D-glucose, D-fructose, D-galactose, D-mannose, DL-arabinose and DL-xylose. The tri-, di- and monosaccharides are among others (but not limited to) from the digestion and depolymerization of cellulose and hemicellulose by suitable methods; - directly from high-sugar plants such as sugar beet, sugar cane,

Sugar Palm, Sugar Maple, Sugar Millet, Silver Date Palm, Honey Palm, Palm Palm and Agave by Extraction; from the depolymerization of vegetable starch by hydrolysis; from the depolymerization of animal glycogen by hydrolysis; directly from milk produced in the dairy industry. In a further preferred embodiment of the invention, exclusively renewable raw materials are used for the fermentative production of isobutene. If desired, the origin of the carbon atoms can be determined from renewable resources by the test method described in ASTM D6866. The ratio of the C ¹⁴ to C ¹² carbon isotopes is determined and compared with the isotope ratio of a reference substance whose carbon atoms come to 100% from renewable raw material sources. This test method is also known in a modified form as the radiocarbon method and is described, inter alia, in Olsson, IU 1991, Euro Courses: Advanced Scientific Techniques, Volume 1, Issue Sei. Dating Methods, pages 15-35. According to a preferred embodiment of the invention, the fermentation process is carried out at temperatures of> 20 ° C to <45 ° C and under atmospheric pressure and releases isobutene as a gaseous product. This embodiment has the advantage that so recovered isobutene can be used immediately or after separation of inerts.

Alternatively, according to an equally preferred embodiment of the invention, the fermentation process is carried out at temperatures of> 20 ° C to <45 ° C and under pressure between 1 to 30 bar. In this case, isobutene can be obtained as a liquid compound and separated by phase separation directly from the fermentation medium. The separation of inerts can be greatly facilitated in this preferred embodiment.

According to a preferred embodiment, step b) is carried out under acid catalysis. Here, e.g. Sulfuric acid or acidic ion exchangers, as they u.a. in Weissermel, Arpe, Industrial Organic Chemistry, VCH Verlagsgesellschaft, 3rd edition, 1988, p. 77; Hydrocarbon Processing, April 1973, p 171-173 are described. Alternatively, the methods described in US2004 / 0054246, US4100220 (A), US4447668 (A) and US5877372 (A) may be used.

The process comprises a further step c), which is carried out according to b): c) purification of the diisobutene, preferably by distillation

Step c) is preferably carried out so that the unreacted volatile components are separated from the diisobutene and the resulting diisobutene is purified by distillation from the optionally formed in small amounts tri-isobutene and higher isobutene oligomers. Tri-isobutene thus obtained and the higher isobutene oligomers thus obtained can likewise be refined to give valuable secondary products. The diisobutene prepared in this way can be further processed in successor reactions, for example in the sense of the hydroformylation reaction or the cooking reaction to isononyl derivatives (Ullmanns Encyklopadie der technischen Chemie, 4th Edition, 1975, Verlag Chemie, Volume 9, pages 144-145).

The above-mentioned and the claimed and described in the embodiments described in accordance with the invention synthesis steps are subject in their technical

Conception no special exceptions, so that in the

Application field known selection criteria can fully apply.

The individual combinations of the components and the features of the already mentioned embodiments are exemplary; the exchange and substitution of these teachings with other teachings contained in this document with the references cited are also expressly contemplated. The person skilled in the art recognizes that variations,

Modifications and other embodiments described herein may also occur without departing from the spirit and scope of the invention. Accordingly, the above description is illustrative and not restrictive. The word "comprising" used in the claims does not exclude other ingredients or steps The indefinite article "a" does not exclude the meaning of a plural. The mere fact that certain measures are recited in mutually different claims does not make it clear that a combination of these dimensions can not be used to advantage. The scope of the invention is defined in the following claims and the associated equivalents.

Claims

PATENT CLAIMS

Process for the preparation of diisobutene, comprising the steps of a) fermentative production of isobutene

b) Dimerization of isobutene to diisobutene

c) Purification of the diisobutene.

The method of claim 1, wherein between step a) and b) no purification of the isobutene.

The method of claim 1 or 2, wherein the isobutene in step a)

Trisaccharides, disaccharides, monosaccharides, acetone or mixtures thereof is obtained.

Process according to claim 1 or 2, wherein renewable raw materials are used for the fermentative production of isobutene.

Method according to one of claims 1 to 4, wherein the fermentation process at temperatures of> 20 ° C to <45 ° C and carried out under atmospheric pressure and isobutene is released as a gaseous product.

6. The method according to any one of claims 1 to 4, wherein the fermentation process at temperatures of> 20 ° C to <45 ° C and under pressure between 1 to 30 bar is performed.

7. The method according to any one of claims 1 to 6, wherein step b) is carried out under acid catalysis. Method according to one of claims 1 to 7, wherein step c) is carried out by distillation.

Use of the diisobutene according to one or more of claims 1 to 8 for the preparation of derivatives which contain compounds with the 3,5,5-trimethylhexyl or 2,2,4,4-tetramethylpentyl radical as the main constituent.