Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2002-07-18
2003-06-03
Barts, Samuel (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S910000, C568S910500
Reexamination Certificate
active
06573414
ABSTRACT:
The present invention relates to a process for preparing C
9
-alcohols and also to a process for the integrated preparation of C
9
-alcohols and C
10
-alcohols.
Fossil fuels and the hydrocarbons obtained therefrom have a double function in industrial synthesis. They serve firstly as energy sources and secondly as raw materials for chemical products. It is frequently customary to burn hydrocarbons obtained as by-products in industrial synthesis or depleted in specific products of value in order to make their energy content available. There is at present a tendency to replace fossil fuels in the energy sector and thus to secure raw materials supply in the long term at a given supply of fossil raw materials. To achieve this, it is necessary to use as much as possible of the components present in the hydrocarbons obtained from fossil raw materials as materials. A difficulty is that hydrocarbon streams are usually obtained as poorly defined mixtures of variable composition in industrial synthesis. The utilization as materials of the components of value present therein frequently founders on the disproportionately high cost of purification or fractionation. It is necessary to devise integrated processes in which the by-products of one process step can be utilized as materials in a further process step without complicated fractionation being required.
It is known that C
4
fractions which are available in large quantities both from FCC plants and from steam crackers and consist essentially of a mixture of butene and butane can be subjected to an oligomerization reaction to produce butene oligomers, in particular octenes. Such a process is described, for example, in DE 4 339 713. This reaction gives the butene oligomers and a butene-depleted C
4
-hydrocarbon stream in which the butenes are diluted by so much butane that the oligomerization of the butenes still present therein is no longer practical.
The octenes are usually hydroformylated to form C
9
-aldehydes and then hydrogenated to give C
9
-alcohols. The C
9
-alcohols have valuable properties as plasticizer alcohols.
The production of synthesis gas by steam reforming or partial oxidation of hydrocarbons is also known (cf. Weissermel, K. and Arpe H. -J., “Industrielle organische Chemie”, VCH, 4th Edition, 1994, pages 19-24.
In Sb. Nauchn. Tr.—Vses. Nauchno-Issled Inst. Pererab. Nefti (1981), 39, 11-20, Gusev I. N. et al. report the preparation of hydrogen by catalytic steam reforming of refinery gases comprising hydrogen, C
1-4
-alkanes and about 20% of alkenes. An upstream hydrogenation step is described as being advantageous.
JP 52132-004 describes the preparation of a gas comprising from 50 to 95 mol % of H
2
, from 1 to 50 mol % of CO, <25 mol % of CO
2
and <25 mol % of methane by treating a hydrocarbon with an NiO catalyst in the presence of steam.
In Nippon Gasu Kyokaishi (1978), 31(8), 21-9, Yokoyama, A. reports results on the catalytic reforming of C
4
-alkanes and a fraction having a high content of C
4
-alkanes and C
4
-alkenes.
It is an object of the present invention to provide a process for preparing C
9
-alcohols and a process for preparing C
9
-alcohols and C
10
-alcohols which start out from C
4
-hydrocarbons and allow very substantial utilization of the feed hydrocarbons as materials.
We have found that this object is achieved by using the butene-depleted C
4
-hydrocarbon stream obtained in butene oligomerization as starting material for the preparation of synthesis gas which can be employed for hydroformylation of the octenes obtained by butene dimerization to form C
9
-aldehydes and/or of butene to form C
5
-aldehydes.
The present invention accordingly provides, in a first aspect, a process for preparing C
9
-alcohols, which comprises
a) providing a C
4
-hydrocarbon stream comprising butene and butane;
b) subjecting the C
4
-hydrocarbon stream to oligomerization over an olefin oligomerization catalyst and fractionating the resulting reaction mixture to give an octene-containing stream and a butene-depleted C
4
-hydrocarbon stream;
c) subjecting the butene-depleted C
4
-hydrocarbon stream to steam reforming or partial oxidation to give carbon monoxide and hydrogen;
d) hydroformylating the octene-containing stream by means of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to form C
9
-aldehydes, where the carbon monoxide used and/or the hydrogen used originate at least in part, e.g. to an extent of more than 50%, preferably to an extent of more than 80%, in particular completely, from step c); and
e) catalytically hydrogenating the C
9
-aldehydes by means of hydrogen.
The hydrogen used in step e) preferably originates at least in part, e.g. to an extent of more than 50%, preferably to an extent of more than 80%, in particular completely, from step c).
The “butene-depleted C
4
-hydrocarbon stream” is depleted in butene compared to the C
4
-hydrocarbon stream used. The amount of butenes present is reduced by a proportion corresponding to the butene conversion in the oligomerization. In general, the butene content of the butene-depleted C
4
-hydrocarbon stream is decreased by from 70 to 99%, usually from 80 to 95%, compared to the C
4
-hydrocarbon stream used. The butene-depleted C
4
-hydrocarbon stream comprises, for example, from 5 to 70 mol %, usually from 5 to 45 mol %, of butene, with the remainder being essentially butane.
The present invention also provides, in a second aspect, a process for the integrated preparation of C
9
-alcohols and C
10
-alcohols, which comprises
a) providing a C
4
-hydrocarbon stream comprising butene and butane;
b) hydroformylating the C
4
-hydrocarbon stream by means of carbon monoxide and hydrogen to form C
5
-aldehydes, so as to give a first butene-depleted C
4
-hydrocarbon stream;
c) subjecting the C
5
-aldehydes to an aldol condensation; and
d) catalytically hydrogenating the products of the aldol condensation by means of hydrogen to form C
10
-alcohols;
e) subjecting the first butene-depleted C
4
-hydrocarbon stream to oligomerization over an olefin oligomerization catalyst and fractionating the resulting reaction mixture to give an octene-containing stream and a second butene-depleted C
4
-hydrocarbon stream;
f) hydroformylating the octene-containing stream by means of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to form C
9
-aldehydes;
g) catalytically hydrogenating the C
9
-aldehydes by means of hydrogen;
h) subjecting the second butene-depleted C
4
-hydrocarbon stream to steam reforming or partial oxidation to give carbon monoxide and hydrogen which are recirculated at least in part to step b) and/or step f).
The hydrogen used in step d) and/or in step g) preferably originates at least in part, e.g. to an extent of more than 50%, preferably to an extent of more than 80%, in particular completely, from step d).
The “first butene-depleted C
4
-hydrocarbon stream” is depleted in butene compared to the C
4
-hydrocarbon stream used, and the “second butene-depleted C
4
-hydrocarbon stream” is depleted in butene compared to the first butene-depleted C
4
-hydrocarbon stream. In general, the butene content of the first butene-depleted C
4
-hydrocarbon stream is reduced by from 25 to 50%, and that of the second butene-depleted C
4
-hydrocarbon stream is reduced by from 70 to 99% compared to the first butene-depleted C
4
-hydrocarbon stream. The first butene-depleted C
4
-hydrocarbon stream comprises, for example, from 30 to 60 mol % of butene and the second butene-depleted C
4
-hydrocarbon stream comprises, for example, from 0.3 to 20 mol % of butene, with the remainder essentially butane.
C
4
-hydrocarbon streams suitable as starting material comprise, for example, from 50 to 99 mol %, preferably from 60 to 90 mol %, of butenes and from 1 to 50 mol %, preferably from 10 to 40 mol %, of butanes. The butene fraction preferably comprises from 40 to 60 mol % of 1-butene, from 20 to 30 mol % of 2-butene and less than 5 mol %, in particular less than 3 mol %, of isobutene (based on the butene fraction). A particularly pref
McAtee Michael Richard
Paciello Rocco
Ulbrich Michael-Dieter
Barts Samuel
BASF - Aktiengesellschaft
Keil & Weinkauf
Price Eluis O.
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