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1. (WO2007003909) PROCESS FOR THE CONVERSION OF SYNTHESIS GAS TO OXYGENATES CONTAINING C2+ ALCOHOLS
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Claims
1. Process for the conversion, of carbon oxide(s) and hydrogen containing feedstocks, into alcohols in the presence of a particulate catalyst characterised by the following steps:

1. converting a carbon oxide(s) and hydrogen feed having a (H2-CO2):(CO+CO2) molar ratio comprised between 0.5 and 2.0, in the presence of a particulate
catalyst in a homologation reactor under a temperature comprised between 150 and 400°C and a pressure of 50 to 250 bar, into a stream A, comprising
essentially alcohol(s), ester(s), H2, CO and CO2,
2. separating the alcohol stream A, into a stream B comprising H2, CO and CO2
and a stream C comprising the alcohol(s) and ester(s),
3. optionally separating the stream B into a H2 and CO2 depleted stream D'
having a (H2-CO2):(CO+CO2) molar ratio of lower than 0.5 and a H2 and CO2 enriched stream D having a (H2-CO2):(CO+CO2) molar ratio higher than 3,
4. converting a CO/CO2/H2 feed (optionally comprising stream D) having a (H2- CO2):(CO+CO2) molar ratio higher than 3 in a methanol reactor into a stream
E comprising essentially methanol, water, H2, CO and CO2,
5. separating stream E into stream F comprising H2, CO and CO2 and stream G
comprising methanol and water,
6. separating stream G into stream H consisting essentially of water and stream I comprising essentially methanol,
7. reintroducing stream I into the homologation reactor of step 1, and
8. recovering a stream C comprising an increased weight content of total ethanol and propanol(s).
2. Process (step 9) according to claim 1 wherein the stream C from step 8 is separated into
- a stream J comprising essentially methanol which is then preferably recycled into the homologation reactor of step 1, and
- a stream K comprising essentially the ethanol and propanol(s) alcohols.
3. Process (step 10) according to claim 1 wherein the recovered stream C from step 8 is separated into
- a stream J comprising essentially methanol which is then preferably recycled into the homologation reactor of step 1, - a stream K comprising essentially the ethanol and propanol(s) alcohols, and
- a stream X comprising essentially the ester(s) which are then preferably recycled into the methanol reactor of step 4.
4. Process for the conversion of hydrocarbons to alcohols comprising the steps of: a. converting hydrocarbon in a syngas reactor into a stream S consisting of a mixture of carbon oxide(s) and hydrogen having a (H2-CO2):(CO+CO2) molar ratio of at least 2,
b. separating stream S into a stream T' having a (H2-CO2):(CO+CO2) molar ratio between 0.5 and 2.0 and a stream T having a (H2-CO2):(CO+CO2) molar ratio higher than 3,
c. using stream T' as the carbon oxide(s) and hydrogen feed source of step 1 of claim 1, and converting it in the homologation reactor into stream A,
d. using stream T as the carbon oxide(s) and hydrogen feed of step 4 of claim 1
(optionally also comprising stream D of step 3 of claim 1), and converting the
(mixed) stream T (and D) in the methanol reactor into stream E, and
e. proceeding with the steps of any of claims 1 to 3.
5. A process for the conversion of hydrocarbon to alcohols according to any of the preceding claims whereby stream F is recycled back into the methanol reactor of step 4.

6. A process for the conversion of hydrocarbon to alcohols according to claims 4 and 5 whereby the (H2-CO2):(CO+CO2) molar ratio of stream S obtained from the syngas reactor is of at least 2, preferably between 2.1 and 3.0 and most preferably between 2.4 and 2.8.
7. A process for the conversion of hydrocarbons to alcohols according to claims 4 to 6 whereby stream T has a (H2-CO2):(CO+CO2) molar ratio of higher than 3, and contains more than 90% moles of H2.
8. A process for the conversion of hydrocarbons to alcohols according to any of the preceding claims whereby the particulate catalyst used in the homologation reactor is a modified molybdenum sulphide based catalyst, and/or a modified methanol based catalyst and/or a modified Fischer-Tropsch catalyst.
9. A process for the conversion of hydrocarbons to alcohols according to any of the preceding claims whereby the catalyst used in the homologation reactor contains at least molybdenum and/or cobalt and/or copper and is preferably promoted by the addition of an alkali metal salt.
10. A process for the conversion of hydrocarbons to alcohols according to any of the preceding claims whereby the resulting product stream from the homologation reactor of step 1 (stream A) is treated so as to remove any sulphur present.
11. A process for the conversion of hydrocarbons to alcohols according to claim 10, whereby the said removal of the sulphur is performed by the use of a sulphur guard bed.

12. A process for the conversion of hydrocarbon to alcohols according to any of the preceding claims whereby the (H2-CO2):(CO+CO2) molar ratio of the feed introduced into the homologation reactor is comprised between 0.5 and 2.0 and preferably comprised between 0.8 and 1.3.
13. A process for the conversion of hydrocarbons to alcohols according to any of the preceding claims whereby the optional separation of step 3 and the separation of step b are respectively performed by using a H2/CO2 membrane.
14. A process for the conversion of hydrocarbons to alcohols according to claim 13 whereby the H2/CO2 membrane are preferably based on a polymer packaged as a hollow fiber.
15. A process for the conversion of hydrocarbons to alcohols according to any of the preceding claims whereby the optional separation under step 3 is performed.
16. A process for the conversion of hydrocarbons to alcohols according to any of claims 4 to 15 whereby stream D' is recycled to the syngas conversion reactor as feedstock and/or fuel and optionally at least part of it is recycled to the homologation reactor.
17. A process for the conversion of hydrocarbons to alcohols according to any of the preceding claims whereby at least part of stream B is also used as a feed to the methanol reactor.
18. A process for the conversion of hydrocarbons to alcohols according to any of the preceding claims whereby at least part of stream J - preferably all of stream J - is recycled back into the homologation reactor.