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Title:
PROCESS TO PREPARE A HYDROCARBON
Document Type and Number:
WIPO Patent Application WO/2008/113766
Kind Code:
A2
Abstract:
The invention is directed to a process to prepare a hydrocarbon product from a gaseous feed comprising methane by (a) converting the gaseous feed (30) by partial oxidation into a first mixture of hydrogen and carbon monoxide (32), (b) converting a liquid or solid biomass feed (35) by partial oxidation into a second mixture of hydrogen and carbon monoxide (37), (c) increasing the hydrogen content (38) of the second mixture (37) to obtain a hydrogen rich mixture (40), (d) performing a Fischer-Tropsch synthesis (33 a-c) using the first mixture as feed to obtain a waxy paraffinic synthesis product (34), (e) performing one or more hydroconversion steps (45) on the waxy paraffinic synthesis product or part of said waxy paraffinic synthesis product to obtain the hydrocarbon product (48), wherein the hydrogen rich mixture is used as additional feed in step (d) (41) and/or reactant in step (e) (44)

Inventors:
BOERRIGTER HAROLD (NL)
EILERS JACOBUS (NL)
VAN SCHIJNDEL JOHANNES MARIE GEMMA (NL)
UNRUH DOMINIK JOHANNES MICHAEL (NL)
Application Number:
PCT/EP2008/053120
Publication Date:
September 25, 2008
Filing Date:
March 14, 2008
Export Citation:
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Assignee:
SHELL INT RESEARCH (NL)
BOERRIGTER HAROLD (NL)
EILERS JACOBUS (NL)
VAN SCHIJNDEL JOHANNES MARIE GEMMA (NL)
UNRUH DOMINIK JOHANNES MICHAEL (NL)
International Classes:
C10G2/00; C01B3/36; C10J3/48; C10J3/84
Domestic Patent References:
WO2006117355A12006-11-09
WO2005005576A12005-01-20
Foreign References:
EP1526165A12005-04-27
US20050187415A12005-08-25
Attorney, Agent or Firm:
SHELL INTERNATIONAL B.V. (P.O. Box 384, CJ THE HAGUE, NL)
Download PDF:
Claims:

C L A I M S

1. Process to prepare a hydrocarbon product from a gaseous feed comprising methane by

(a) converting the gaseous feed by partial oxidation into a first mixture of hydrogen and carbon monoxide, (b) converting a liquid or solid biomass feed by partial oxidation into a second mixture of hydrogen and carbon monoxide,

(c) increasing the hydrogen content of the second mixture to obtain a hydrogen rich mixture, (d) performing a Fischer-Tropsch synthesis using the first mixture as feed to obtain a waxy paraffinic synthesis product,

(e) performing one or more hydroconversion steps on the waxy paraffinic synthesis product or part of said waxy paraffinic synthesis product to obtain the hydrocarbon product, wherein the hydrogen rich mixture is used as additional feed in step (d) and/or as reactant in step (e) .

2. Process according to claim 1, wherein the partial oxidation of step (b) is performed by contacting an oxygen containing gas with the liquid or solid biomass feed in a burner of a pressurized and entrained gasification reactor and wherein the second mixture thus obtained in said burner having a temperature between 1000 and 1800 0 C is reduced in temperature to a temperature between 160 and 330 0 C by direct contacting the second mixture with liquid water thereby obtaining a second mixture having a content of water and a stream of used liquid water.

3. Process according to any one of claims 1-2, wherein the content of hydrogen in step (c) is increased by performing one or more water gas shift reaction steps .

4. Process according to claim 3, wherein the content of hydrogen in the hydrogen rich mixture is further increased in a pressure swing absorber, membrane separation or combinations of such processes.

5. Process according to any one of claims 1-4, wherein in step (b) a solid biomass is used as feed which biomass is obtained by torrefaction of a biomass source.

6. Process according to any one of claims 1-4, wherein in step (b) a liquid biomass is used as feed which biomass is obtained by flash pyrolysis of a biomass source . 7. Process according to anyone of claims 1 to 6, wherein the hydrocarbon product is a naphtha, kerosene, gas oil, base oil and/or base oil.

8. Process according to any one of claims 2-7, wherein the minerals as present in the used liquid water are isolated and used as fertiliser or soil improver when growing a biomass source from which the biomass feed is obtained.

9. Process to prepare a mixture of hydrogen and carbon monoxide from by partial oxidation by contacting an oxygen containing gas with the liquid or solid biomass feed in a burner of a pressurized and entrained gasification reactor and wherein the mixture of hydrogen and carbon monoxide thus obtained in said burner is reduced in temperature by direct contacting this mixture with liquid water thereby obtaining a second mixture having a content of water and a stream of used liquid water and wherein the minerals as present in the used liquid water are isolated and used as fertiliser or soil

improver when growing a biomass source from which the biomass feed is obtained.

10. Process according to claim 9, wherein a solid biomass is used as feed which biomass is obtained by torrefaction of a biomass source.

11. Process according to claim 9, wherein a liquid biomass feed is used as feed which biomass feed is a biomass slurry comprising flash pyrolysis oil and flash pyrolysis char as obtained when performing a flash pyrolysis process on a biomass source.

12. Process to prepare a hydrogen rich mixture from a biomass feed by converting a liquid or solid biomass feed by partial oxidation into a mixture of hydrogen and carbon monoxide, wherein the partial oxidation is performed by contacting an oxygen containing gas with the liquid or solid biomass feed in a burner of a pressurized and entrained gasification reactor and wherein the second mixture thus obtained in said burner having a temperature between 1000 and 1800 0 C is reduced in temperature to a temperature between 160 and 330 0 C by direct contacting the second mixture with liquid water thereby obtaining a second mixture having a content of water and increasing the hydrogen content of the second mixture by performing one or more water gas shift reaction steps to obtain a hydrogen rich mixture.

Description:

PROCESS TO PREPARE A HYDROCARBON

The invention is directed to a process to prepare a hydrocarbon from a gaseous feed comprising methane.

Such a process is described in WO-A-2006/056594. In this publication a process is described for making normally liquid and optionally normally solid hydrocarbons. The process comprises a partial oxidation step using natural gas as feed to obtain a synthesis gas stream. The synthesis gas is used as feed for a Fischer- Tropsch conversion of the synthesis gas stream over a cobalt catalyst. The Fischer-Tropsch products are a stream of normally liquid and optionally normally solid hydrocarbons. In this step also an off-gas stream comprising unconverted carbon monoxide, unconverted hydrogen, C1-C4 hydrocarbons is obtained. This off-gas is hydrogenated in the presence of a Cu/ZnO catalyst and steam reformed to prepare hydrogen. This hydrogen is used for the upgrading of the normally liquid and optionally normally solid hydrocarbons, e.g. hydrogenation, hydroisomerisation and/or hydrocracking, hydrodesulphurisation . Alternatively hydrogen is used for increasing the H2/CO ratio of the syngas stream before the syngas is used in the Fischer-Tropsch synthesis .

A disadvantage of the process of WO-A-2006/056594 is that complicated measures have to be taken to make the Fischer-Tropsch off-gas suited as a feed for the steam methane reformer in order to prepare hydrogen.

The object of the present invention is to provide an alternative process.

The following process achieves this aim. Process to prepare a hydrocarbon product from a gaseous feed comprising methane by

(a) converting the gaseous feed by partial oxidation into a first mixture of hydrogen and carbon monoxide,

(b) converting a liquid or solid biomass feed by partial oxidation into a second mixture of hydrogen and carbon monoxide,

(c) increasing the hydrogen content of the second mixture to obtain a hydrogen rich mixture,

(d) performing a Fischer-Tropsch synthesis using the first mixture as feed to obtain a waxy paraffinic synthesis product,

(e) performing one or more hydroconversion steps on the waxy paraffinic synthesis product or part of said waxy paraffinic synthesis product to obtain the hydrocarbon product, wherein the hydrogen rich mixture is used as additional feed in step (d) and/or as reactant in step (e) . Applicants found that by using a biomass feed to prepare hydrogen the recycle of the Fischer-Tropsch off- gas can be avoided or at least limited. A further advantage is that a more sustainable process with regard to carbon dioxide emissions is obtained because any carbon dioxide by-product obtained in the process to prepare hydrogen has a biomass source. The invention is particularly advantageous in countries where both natural gas resources and large quantities of biomass are available. Examples of such regions are the tropical regions which are both rich in hydrocarbon resources as well as rich in abundant biomass growth.

The gaseous feed used in step (a) is preferably natural gas. The feed comprises more than 70 v/v% methane

and more preferably more than 90 v/v/% methane. The partial oxidation in step (a) may be performed in combination with a reforming catalyst in a so-called auto-thermal reformer. Preferably the partial oxidation is performed in the absence of a downstream reformer catalyst, i.e. in a so-called non-catalyzed partial oxidation. A well known example of such a process is the Shell Gasification Process as described in the Oil and Gas Journal, September 6, 1971, pages 68-90.

CH 4 + O 2 ► CO + H 2 O + H 2

2CH 4 + O 2 ^ 2CO + 4H 2

CO + H 2 O ^CO 2 + H 2 (1)

The combination of the three reactions (1) results in a H 2 /CO ratio of 1.6 - 1.8. Thus to provide the preferred

H 2 /CO ratio of between 2 and 2.1 hydrogen as obtained in step (c) is preferably mixed with the effluent of step (a) . In step (b) a liquid and/or solid biomass feed is converted by partial oxidation into a second mixture of hydrogen and carbon monoxide. A suitable solid biomass feed is obtained by drying and torrefaction of a biomass source. Torrefaction is a thermal treatment performed at relatively longer residence time in the absence of added molecular oxygen of the biomass source, preferably at a temperature of between 200 and 300 0 C. Torrefaction is preferably combined with a compression or pelletation step in order to make the biomass feed more suited for a gasification process wherein the biomass feed is supplied in a so-called dry form. Torrefaction of biomass source

material is well known and for example described in M. Pach, R. Zanzi and E. Bjδrnbom, Torrefied Biomass a Substitute for Wood and Charcoal, 6th Asia-Pacific International Symposium on Combustion and Energy Utilization, May 2002, Kuala Lumpur and in Bergman,

P. C.A., "Torrefaction in combination with pelletisation - the TOP process", ECN Report, ECN-C-05-073, Petten, 2005.

A suitable liquid biomass is obtained by drying and flash pyrolysis of a biomass source. In flash pyrolysis processes a solid char and a liquid biomass feed component is typically obtained. The present invention is directed to embodiments wherein only the liquid biomass feed component is used as feed or wherein a mixture of the char and the liquid biomass feed component, a so- called biomass slurry, is used as the liquid biomass feed. Flash pyrolysis is well known and for example described in EP-A-904335; in Dinesh Mohan, Charles U. Pittman, Jr., and Philip H. Steele. Pyrolysis of Wood/Biomass for Bio-oil: A Critical Review. Energy & Fuels 2006, 20, 848-889; and in E. Henrich: Clean syngas from biomass by pressurised entrained flow gasification of slurries from fast pyrolysis. In: Synbios, the syngas route to automotive biofuels, conference held from 18-20 May 2005, Stockholm, Sweden (2005) .

It may be advantageous to have the biomass in step (b) in a liquid state. In the liquid state the biomass is more easily increased in pressure to the preferred elevated pressure levels of the partial oxidation reaction. Such a liquid state may be achieved for solid biomass, like obtained by torrefaction, by mixing the solid biomass with a liquid hydrocarbon oil. This hydrocarbon oil may be mineral derived oil, for

example the residual oil obtained when refining crude mineral oils, vegetable oils, like for example palm oil or the pyrolysis oil as described above. Alternatively the above pyrolysis oil as obtained from biomass may be combined with non-biomass solid carbonaceous feeds such as for example coal.

Suitable biomass sources are all solid materials produced by photosynthesis. Examples of such solid materials are wood, straw, grasses, (micro) algae, weeds or residues of the agricultural industry, such as the palm oil industry, corn industry, bio-diesel industry, forestry industry, and the related wood processing industry and paper industry.

In step (b) a liquid or solid biomass feed is converted by partial oxidation into a second mixture of hydrogen and carbon monoxide . Such a partial oxidation process may be any process suited for converting biomass into a hydrogen-comprising stream. Examples of suitable partial oxidation processes are processes which utilize a fluidised bed gasifier or a circulating fluidised bed gasifier. More preferably partial oxidation is carried out in a so-called entrained gasifier. In such a gasifier the feed is partially oxidized in a flame exiting a burner to which feed and an oxidiser gas is fed, optionally with a moderator gas and optional fluxing agents. In case of shortfall of biomass feed the partial oxidation step (b) is preferably and temporally performed using an alternative feedstock, suitably the same gaseous feed used in step (a) . A suited method for performing step (b) starting from liquid biomass feed is by performing a partial oxidation on said biomass feed using a multi-orifice burner provided with an arrangement of separate passages,

wherein the biomass feed flows through a passage of the burner, an oxidiser gas flows through a separate passage of the burner and wherein the passage for biomass feed and the passage for oxidiser gas are separated by a passage through which a moderator gas flows. Preferably the exit velocity of the moderator gas is greater than the exit velocity of the oxidiser gas.

Applicants found that it is possible to convert a liquid and ash containing biomass feed to a mixture of carbon monoxide and hydrogen by means of partial oxidation. Applicants found that by operating the multi- orifice burner in the manner as claimed an improved burner life-time is achieved. For similar viscosity type feeds a substantially improved lifetime is observed when compared to burners operating under the conditions of the state of the art process. Furthermore less temperature fluctuations are observed in the reactor when performing the process of the invention. This is an indication that less flame mode changes are present. Frequent changes in flame modes are indicative for an operation wherein burner damage may occur .

Without wishing to be bound to the following theory applicants believe that the more stable and less damaging operation of the burner results by using a moderator gas having a high velocity as a separate medium between oxidiser gas and biomass feed. The moderator gas will break up the biomass feed and act as a moderator such that reactions in the recirculation zone at the burner tips are avoided. The result will be that the hydrocarbon droplets will only come in contact with the oxidiser gas at some distance from the burner surface. It is believed that this will result in less burner damage, e.g. burner

tip retraction. The invention and its preferred embodiments will be further described below.

As explained above the relative velocity of the biomass feed and the moderator gas is relevant for performing the present invention. Preferably the exit velocity of the moderator gas is at least 5 times the velocity of the biomass feed in order to achieve a sufficient break up of the liquid feed. Preferably the exit velocity of the biomass feed is between 2 and 40 m/s and more preferably between 2 and 20 m/s. The exit velocity of the moderator gas is preferably between 40 and 200 m/s, more preferably between 40 and 150 m/s. The exit velocity of the oxidiser gas is preferably between 30 and 120 m/s, more preferably between 30 and 70 m/s. The respective velocities are measured or calculated at the outlet of the said respective channels into the gasification zone.

Oxidiser gas comprises air or (pure) oxygen or a mixture thereof. With pure oxygen is meant oxygen having a purity of between 95 and 100 vol%. As moderator gas preferably steam, water or carbon dioxide or a combination thereof is used. More preferably steam is used as moderator gas .

The multi-orifice burner is provided with an arrangement of separate, preferably co-annular passages. Such burner arrangements are known and for example described in EP-A-545281 or DE-OS-2935754. Usually such burners comprise a number of slits at the burner outlet and hollow wall members with internal cooling fluid (e.g. water) passages. The passages may or may not be converging at the burner outlet. Instead of comprising internal cooling fluid passages, the burner may be provided with a suitable ceramic or refractory lining

applied onto or suspended by a means closely adjacent to the outer surface of the burner (front) wall for resisting the heat load during operation or heat-up/shut down situations of the burner. Advantageously, the exit(s) of one or more passages may be retracted or protruded.

The burner preferably has 4, 5, 6 or 7 passages. In a preferred embodiment the burner has 6 or 7 passages. In an even more preferred embodiment the burner has 7 passages wherein a shielding gas flows through the outer most passage at a velocity of between 5 and 40 m/s. The shielding gas is preferably the same gas as used for the moderator gas . In the embodiment wherein the number of passages are 7, preferably the following streams flow through the below listed passages: an oxidiser flow through the inner most passage 1 and passage 2, a moderator gas flow through passage 3, a biomass feed flow through passage 4, a moderator gas flow through passage 5, an oxidiser flow through passage 6, and a shielding gas flow through outer most passage 7, preferably at a velocity of between 5 and 40 m/s.

Alternatively the number of passages is 6 wherein the passage 1 and 2 of the above burner is combined or wherein the passage 7 is omitted.

When starting from a solid biomass feed the partial oxidation is preferably performed in an entrained gasifier, such as the gasifier known from the Shell Coal Gasification Process. Suitable reactor and burner configurations related to the Shell Coal Gasification Process and to other possible processes are for example described in WO-A-2006117355, US-A-4887962, US-A-4523529,

and US-A-4510874. The reactor provided with a burner for liquid feeds as described above and a burner for solids feeds may advantageously be provided in a reactor configuration as described below and illustrated in Figure 1.

Step (b) is preferably performed at a syngas product outlet temperature of between 1000 and 1800 0 C and more preferably at a temperature between 1200 and 1500 0 C. The pressure of the mixture of carbon monoxide and hydrogen as prepared is preferably between 0.3 and 12 MPa and preferably between 2 and 8 MPa. The ash components as present in the feed will form a so-called liquid slag at these temperatures. The slag will preferably form a layer on the inner side of the reactor wall, thereby creating a isolation layer. The temperature conditions are so chosen that the slag will create a layer and flow to a lower positioned slag outlet device in the reactor. Additional fluxing agent may be supplied to the burner in order to increase the slag layer. The slag outlet device is preferably a water bath at the bottom of the gasification reactor to which the slag will flow due to the forces of gravity .

The temperature of the syngas is preferably reduced by directly contacting the hot gas with liquid water in a so-called quenching step. This is preferred because the composition of biomass feed is such that it results in a gas mixture after partial oxidation containing volatile inorganic compounds. These volatile compounds are easily removed from the gas by contacting this gaseous mixture directly with water. Direct quenching with water further has the advantage that the syngas will increase in steam content, which is required when performing a preferred water gas shift reaction in step (c) .

The direct contacting with liquid water is preferably preceded by injecting water into the flow of syngas steam. This water may be fresh water. In a preferred embodiment a solids containing water may partly or wholly replace the fresh water. Preferably the solids containing water is obtained in the water quenching zone and/or from a possible downstream scrubber unit, for example a bleed stream of the scrubber unit. Use of a solids containing water as here described has the advantage that water treatment steps may be avoided or at least be limited.

The temperature of the synthesis gas after the water quench step is preferably between 130 and 330 0 C, more preferably between 160 and 240 0 C.

The slag containing water as obtained in the above quenching step will contain minerals originating from the biomass feed. Especially biomass feed as obtained by torrefaction or the above referred to biomass slurry may contain substantial amounts of minerals, such as for example K, P, Zn, Mg, B, Cu, as well as phosphor. It is preferred to isolate these minerals and reuse them as fertiliser and or soil improver when growing the biomass source. In this manner a mineral recycle is achieved wherein the quality of the land on which the biomass source is produced can be maintained. Such a mineral recycle is of course generally applicable for processes which prepare a mixture of hydrogen and carbon monoxide from a biomass feed using the above partial oxidation process .

The process is preferably performed in a reactor vessel as illustrated in Figure 1. The Figure shows a gasification reactor vessel (1), which, when in use, is provided at its upper end with a downwardly directed multi-orifice burner (2). In use vessel (1) is vertically

oriented. Reference to terms like upper, lower, bottom, top, vertical and horizontal relate to this vertical orientation of the reactor vessel (1) as shown in Figure 1. Burner (2) is provided with supply conduits for the oxidiser gas (3), the biomass feed (4) and the moderator gas (5). The burner (2) is preferably arranged at the top end of the reactor vessel (1) pointing with its outlet in a downwardly direction. It may be advantageous, in order to increase the capacity of the reactor, to position two or more horizontally firing burners in the combustion chamber (6) . Preferably four or six burner openings are present at the same horizontal level in the wall of the combustion chamber (6), which openings are evenly distributed along the circumferential of the tubular wall of the combustion chamber (6) . In this manner pairs of diametrical positioned burners are achieved. Alternatively the pairs of burners may be located at different horizontal planes. The pairs of burners may be configured in a staggered configuration relative to a pair at another elevation. In such an embodiment up to and including 8 burners may be present at two or more different horizontal planes. Combinations of downward top firing as shown in Figure 1 and side firing as described above are also possible. The vessel (1) preferably comprises a combustion chamber (6) in the upper half of the vessel provided with a product gas outlet (7) at its bottom end and an opening for the outlet of the burner (2) at its top end. Between the combustion chamber (6) and the wall of vessel (1) an annular space (9) is provided. The wall of the combustion chamber protects the outer wall of vessel (1) against the high temperatures of the combustion chamber (6) . The combustion chamber (6) is preferably provided with a

refractory lined wall (8) in order to reduce the heat transfer to the combustion chamber wall. The refractory wall (8) is preferably provided with means to cool said refractory wall. Preferably such cooling means are conduits (10) through which water flows. Such conduits may be arranged as a spirally wound design in said tubular formed refractory wall (8). Preferably the cooling conduits (10) are arranged as a configuration of parallel-arranged vertical conduits, which may optionally have a common header at their top (11) and a common distributor at their bottom (12) for discharging and supplying water respectively from the cooling means. The common header (11) is fluidly connected to a steam discharge conduit (13) and the common header (12) is fluidly connected to a water supply conduit (14) . More preferably the cooling conduits (10) are interconnected such that they form a gas-tight combustion chamber (6) within the refractory wall. Such interconnected conduits type walls are also referred to as a membrane wall. The cooling by said conduits (10) may be achieved by just the cooling capacity of the liquid water, wherein heated liquid water is obtained at the water discharge point. Preferably cooling is achieved by also evaporation of the water in the conduits (10) . In such an embodiment the cooling conduits are vertically arranged as shown in Figure 1 such that the steam as formed can easily flow to the common header (11) and to a steam outlet conduit (13) of the reactor vessel (1). Evaporation is preferred as a cooling method because the steam may find use in other applications in the process, such as process steam for shift reactions, heating medium for liquid feed or, after external superheating, as moderator gas in the burner according to the process according to the present

invention. A more energy efficient process is so obtained .

Product gas outlet (7) of the combustion chamber (6) is fluidly connected to a dip-tube (16) . Dip-tube (16) is partly submerged in a water bath (20) located at the lower end of the reactor vessel (1). Preferably at the upper end of the dip-tube (16) injecting means (18) are present to add a quenching medium to the, in use, downwardly flowing hot product gas, i.e. the mixture of hydrogen and carbon monoxide. The dip-tube (16) is preferably vertically aligned with the combustion chamber (6) and tubular formed.

The water quenching zone (19) is present in the pathway of the hot product gas as it is deflected at lower outlet (17) of dip-tube (16) in an upwardly direction (see arrows) to flow upward through, an annular space (21) formed between the wall draft tube (22) and dip-tube (16) . In water quenching zone (19) a water level (25) will be present. Above said water level (25) one or more product gas outlet (s) (26) are located in the wall of reactor vessel (1) to discharge the quenched product gas. Partition wall (27) may separate the annular space (9) and the space above water level (25).

At the lower end of the gasification reactor (1) a slag discharge opening (28) is suitably present. Through this discharge opening (28) slag together with part of the water is discharged from the vessel by well known slag discharge means, such as sluice systems as for example described in US-A-4852997 and US-A-67559802. The draft tube (22) envelopes the dip-tube (16) and preferably extends, in use, downwardly within the water quenching zone (19) to a level below that at which the lower extremity of the dip-tube (16) terminates. The hot

product gas is deflected at outlet (17) in an upwardly direction (see arrows) to flow upward through, the annular space (21) formed between the draft tube (22) and dip-tube (16) . By having a draft tube (22) a better defined circulation of water is achieved wherein water flows upwards via annular space (21) and downwards via annular space (24) as present between vessel wall and draft tube (22). This is advantageous for cooling both the hot gas and the wall of the dip-tube (16) . Such a draft tube is for example described in US-A-4605423.

The invention is also directed to a process to prepare a mixture of hydrogen and carbon monoxide from by partial oxidation by contacting an oxygen containing gas with the liquid or solid biomass feed as described above in a burner of a pressurized and entrained gasification reactor and wherein the mixture of hydrogen and carbon monoxide thus obtained in said burner is reduced in temperature by direct contacting this mixture with liquid water as described above thereby obtaining a second mixture having a content of water and a stream of used liquid water.

Step(c) is preferably performed as a catalytic water shift conversion reaction. Suitably by performing one or more water gas shift reaction steps. These processes provide a hydrogen enriched, often highly enriched, gas. The water shift conversion reaction is well known in the art. Generally, water, usually in the form of steam, is mixed with the gas to form carbon dioxide and hydrogen. The catalyst used can be any of the known catalysts for such a reaction, including iron, chromium, copper and zinc. Copper on zinc oxide is a known shift catalyst. Preferably a high temperature shift process and catalyst is used, more preferably an iron/chromium comprising

catalyst is used. A very suitable source for the water is the water of the water quench as described for step (b) . The shifted gas is preferably further enriched, i.e. purified, in hydrogen if used in step (e) by means of a pressure swing absorber, membrane separation or combinations of such processes.

In step (d) a Fischer-Tropsch synthesis is performed using the first mixture as feed to obtain a waxy paraffinic synthesis product. Preferably a first mixture in combination with all or part of the hydrogen rich mixture of step (c) wherein the content of the hydrogen rich mixture in such combined gas composition is chosen such that the H2/CO molar ratio is between 2 and 2.1.

The Fischer-Tropsch synthesis is well known to those skilled in the art and involves synthesis of hydrocarbons from a gaseous mixture of hydrogen and carbon monoxide, by contacting that mixture at reaction conditions with a Fischer-Tropsch catalyst.

Products of the Fischer-Tropsch synthesis may range from methane to heavy paraffinic waxes. Preferably, the production of methane is minimised and a substantial portion of the hydrocarbons produced have a carbon chain length of a least 5 carbon atoms . Preferably, the amount of C5+ hydrocarbons is at least 60% by weight of the total product, more preferably, at least 70% by weight, even more preferably, at least 80% by weight, most preferably at least 85% by weight.

Fischer-Tropsch catalysts are known in the art, and typically include a Group VIII metal component, preferably cobalt, iron and/or ruthenium, more preferably cobalt. Typically, the catalysts comprise a catalyst carrier. The catalyst carrier is preferably porous, such

as a porous inorganic refractory oxide, more preferably alumina, silica, titania, zirconia or mixtures thereof.

The optimum amount of catalytically active metal present on the carrier depends inter alia on the specific catalytically active metal. Typically, the amount of cobalt present in the catalyst may range from 1 to 100 parts by weight per 100 parts by weight of carrier material, preferably from 10 to 50 parts by weight per 100 parts by weight of carrier material. The catalytically active metal may be present in the catalyst together with one or more metal promoters or co- catalysts. The promoters may be present as metals or as the metal oxide, depending upon the particular promoter concerned. Suitable promoters include oxides of metals from Groups HA, IHB, IVB, VB, VIB and/or VIIB of the Periodic Table, oxides of the lanthanides and/or the actinides. Preferably, the catalyst comprises at least one of an element in Group IVB, VB and/or VIIB of the Periodic Table, in particular titanium, zirconium, manganese and/or vanadium. As an alternative or in addition to the metal oxide promoter, the catalyst may comprise a metal promoter selected from Groups VIIB and/or VIII of the Periodic Table. Preferred metal promoters include rhenium, platinum and palladium. A most suitable catalyst comprises cobalt as the catalytically active metal and zirconium as a promoter. Another most suitable catalyst comprises cobalt as the catalytically active metal and manganese and/or vanadium as a promoter . The promoter, if present in the catalyst, is typically present in an amount of from 0.1 to 60 parts by weight per 100 parts by weight of carrier material. It will however be appreciated that the optimum amount of

promoter may vary for the respective elements which act as promoter. If the catalyst comprises cobalt as the catalytically active metal and manganese and/or vanadium as promoter, the cobalt : (manganese + vanadium) atomic ratio is advantageously at least 12:1.

The Fischer-Tropsch synthesis is preferably carried out at a temperature in the range from 125 to 350 0 C, more preferably 175 to 275 0 C, most preferably 200 to 260 0 C. The pressure preferably ranges from 5 to 150 bar abs . , more preferably from 5 to 80 bar abs .

The Fischer-Tropsch synthesis is preferably carried out in a fixed bed reactor or alternatively in a slurry phase regime or an ebullating bed regime, wherein the catalyst particles are kept in suspension by an upward superficial gas and/or liquid velocity. A skilled person will know how to perform the Fischer-Tropsch synthesis based on the many publications describing the said synthesis using such catalysts.

In step (e) a hydroconversion step is performed on the waxy paraffinic synthesis product or part of said waxy paraffinic synthesis product to obtain a saturated and optionally hydroisomerized paraffinic product, wherein the hydrogen rich mixture is used as additional feed in step (c) and/or as reactant in step (e) . Suitable hydroconversion processes are described in EP-A-1641897.

Figure 2 illustrates a possible line-up of the process according to the present invention. In Figure 2 a process line-up is shown wherein a gaseous feed comprising methane (30) is converted by partial oxidation into a first mixture of hydrogen and carbon monoxide (32) in 4 parallel operated reactors (31a-d).

Figure 2 also shows process step (b) wherein a liquid or solid biomass feed (35) is converted into a second

mixture of hydrogen and carbon monoxide (37) by partial oxidation in a reactor (36) . The hydrogen content of the second mixture (37) is increased in shift reactor (38) to obtain a hydrogen rich mixture (40) . The hydrogen content in hydrogen rich mixture (40) can be controlled by increasing or decreasing by-pass (39). Part (41) of hydrogen rich mixture (40) is separately combined as streams (41a-c) with first mixtures (32a-c) . This separately combining is advantageous because the H2/CO molar ratio can then be tailored for each Fischer-Tropsch synthesis reactor (33a-c) by adding more or less of the hydrogen rich mixture to first mixtures (32a-c) . The combined mixture is provided to 3 parallel-operated Fischer-Tropsch synthesis reactors (33a-33c) to obtain a waxy paraffinic synthesis product (34) .

Part (42) of the hydrogen rich mixture (40) is further purified in Pressure Swing Absorber (43) to obtain hydrogen stream (44).

The waxy paraffinic synthesis product (34) is subjected to a hydroconversion step in a hydroisomerisation/hydrocracking reactor (45) using the hydrogen stream (44) as source of hydrogen. In reactor (45) a cracked effluent (46) is obtained which cracked effluent (46) is separated into various hydrocarbon products (48), suitably one or more of the following hydrocarbon products: naphtha, kerosene, gas oil and base oil (48a-d). Suitably the pour point of the base oil product (48d) can be further decreased by means of a solvent or more preferably a catalytic dewaxing step (49) to obtain dewaxed base oil (50) . In case of a catalytic dewaxing step hydrogen stream (44) is suitably used as the source of hydrogen to perform such a process. In Figure 2 a certain number of parallel operated reactors

(31) and (33) are shown. It will be clear to the skilled person that the number of parallel operated reactors may vary and that the relative ratio of the numbers of parallel operated reactors (31) and (33) may also deviate from the ratio as shown. The actual number and ratio will depend on the capacities for reactors (31) and (33) which vary per technology and development.

The invention is also directed to a process to prepare a hydrogen rich mixture from a biomass feed as described above in more detail.