WO2010104467A1

WO2010104467A1 - Oxygenated hydrocarbon reforming

Info

Publication number: WO2010104467A1
Application number: PCT/SG2009/000084
Authority: WO
Inventors: Shici Duan; Luwei Chen; Fabing Su; Jianyi Lin; Chuanhua He; Christoph Weckbecker; Klaus Huthmacher
Original assignee: Agency For Science, Technology And Research; Evonik Degussa Gmbh
Priority date: 2009-03-10
Filing date: 2009-03-10
Publication date: 2010-09-16

Abstract

The present invention provides a method of reforming oxygenated hydrocarbons, especially glycerol, at temperatures of at least 380 C using a Group VIIIB catalyst, to yield methanol. The method provides a direct route to methanol and there is no requirement to gasify the oxygenated hydrocarbon and subsequently synthesize methanol from the synthesis gas. This represents an efficient route to methanol and provides an economically and environmentally sound way of addressing the problem of utilising glycerol formed as a by-product from biodiesel formation.

Description

Oxygenated Hydrocarbon Reforming

Technical Field of the Invention

The present invention is concerned with methods of oxygenated hydrocarbon reforming and in particular methods of glycerol reforming to produce methanol.

Background

Due to the depletion of limited fossil fuel resources and environmental problems caused by burning fossil fuel, biomass has received much more attention recently as a cleaner alternative energy source. Biomass is not only renewable and therefore sustainable, but also carbon dioxide neutral because carbon dioxide emitted from utilization of biomass will be reused by growing biomass through photosynthesis.

It is estimated that biomass could realistically supply 15% of the world's energy. Biodiesel is one major product from biomass besides bioethanol. The world production of biodiesel has increased continuously in recent years, for example, from 2.5 million tons in 2004 to 9 million tons in 2007.

Biodiesel is commonly produced by the transesterification of the vegetable oil or animal fat feedstock. Chemically, transesterified biodiesel comprises a mix of mono- alkyl esters of long chain fatty acids. Methanol is most commonly used to produce methyl esters as it is the cheapest alcohol available.

CH₂OCOR¹ H₂-COH R¹COOCH₃

I

CH₂OCOR" + 3CH₃OH H-C-OH + R¹¹COOCH₃

CH₂OCOR¹" H₂-C-OH R-COOCH₃

Fat/Oil Methanol Glycerol Biodiesel 100 lbs 10 lbs 10 lbs 100 lbs

As shown in the above formula, about 10% glycerol is produced as a major byproduct of biodiesel production. With increasing biodiesel productions in the world, more and more glycerol is being produced. This will greatly exceed the current demand of glycerol. Therefore, the development of new technologies to utilise glycerol is desirable. The usage of low-grade quality glycerol obtained from biodiesel production is a big challenge as this glycerol cannot be used for direct food and cosmetic uses.

One simple way of utilizing glycerol is steam reforming, in which glycerol is converted into synthesis gas, i.e., hydrogen and carbon monoxide. Synthesis gas can then be converted easily into methanol, which can be reused in the reaction of biodiesel production.

Fat/Oil + CH₃OH ^C₃H₈O₃ + Biodiesel

H₂ + CO

By way of an example of the utilisation of glycerol, US5276181 describes a catalytic method of hydrogenating glycerol. It provides for glycerol to be placed in contact with hydrogen and made to react therewith in the presence of a base and a ruthenium catalyst modified with sulphides, at a temperature 270 ⁰C and a pressure of 130 bars.

The major products are oxygenated compounds having from 1 to 3 carbon atoms, particularly 1 ,2-propandiol and lactic acid. However, methanol production from glycerol hydrogenating is extremely low.

As noted above, the production of synthesis gas via steam reforming of glycerol has been reported. For example, US2005/020797A1 describes a method of producing hydrogen from glycerol and other oxygenated hydrocarbons. The method takes place in the condensed liquid phase. The method includes the steps of reacting water and a water-soluble oxygenated hydrocarbon in the presence of a metal catalysts and the catalyst contains a metal from the group of Group VIIIB transition metals.

WO2008/028670 discloses a process for the production of synthesis gas via vapour phase reforming of oxygenated hydrocarbons, particularly glycerol, over Ni, Co, Pt, Pd, Ir, Rh₁ and Ru catalysts. The reaction temperature is in the range of 270-380 ⁰C and pressure is 10-30 bars. Recently, US7388034B1 , claims a two-step process of methanol production from crude glycerol. The crude glycerol stream is combined with superheated steam and oxygen to produce synthesis gas first. Then synthesis gas is passed to a methanol synthesis reaction zone to produce methanol. Autothermal glycerol reforming reaction is run at a temperature of 816°C to 1038⁰C (1500⁰F to 1900⁰F) and a pressure of 200 to 600 psig. Then synthesis gas stream is cooled to a temperature of 182°C to 27°C (36O⁰F to 8O⁰F). Synthesis gas stream is introduced to methanol synthesis reactor at 149°C to 299°C (300⁰F to 57O⁰F) and 500 to 1500 psig. The claimed catalyst for methanol synthesis from synthesis gas is a copper-based catalyst.

US2007/0225383A1 also discloses a two-step process wherein glycerol is converted to synthesis gas and the synthesis gas subsequently subjected to a Fischer-Tropsch reaction to form methanol, albeit at very low yields and selectivity.

US2007/0225383A1 proposes that the two reactions can be combined in a single reactor, equipped with appropriate catalysts for both reactions, and that the heat generated from one reaction is used to drive the other reaction. The reaction temperature 275°C (548K) is selected so as to permit both reactions to proceed in the same reactor.

Summary of the Invention

The present invention provides a new pathway of direct methanol production from vapour or aqueous reforming of oxygenated hydrocarbons, particularly glycerol. In embodiments, large amounts of methanol are produced directly and condensed in the liquid phase after the reforming reaction.

The direct production of methanol from oxygenated hydrocarbon reforming has great economic advantage compared with conventional methods of methanol production from glycerol via synthesis gas, because it avoids the step of methanol synthesis from hydrogen and carbon monoxide.

At its most general, the present invention proposes that direct methanol production from oxygenated hydrocarbons, particularly glycerol, can be achieved by contacting the oxygenated hydrocarbon and water with a suitable catalyst at a temperature above a certain threshold. In this way, the present inventors have found that the reaction pathway is such as to permit direct formation of methanol, rather than gasification (i.e. formation of synthesis gas).

In a first aspect, the present invention provides a method of producing methanol by oxygenated hydrocarbon reforming, the method comprising the step of contacting the oxygenated hydrocarbon and water with a Group VIIIB catalyst at a reaction temperature of at least 380⁰C, to yield methanol.

The present inventors have found that the selection of a temperature of at least 38O⁰C, together with the use of a Group VIIIB catalyst and the presence of water, has a significant influence on the reaction pathway. In particular, the combination of the temperature, catalyst and water as described herein provides a new pathway to methanol. Without wishing to be bound by hypothesis, the present inventors consider that C-C cleavage is favoured over C-H or O-H cleavages so that the reaction stops at methanol production without further decomposition to CO and H₂.

As will be discussed below with respect to the examples, exemplary methods of the present invention provide surprisingly high levels of conversion and selectivity for methanol. This represents a valuable contribution to the art. In particular, the ability to access methanol directly, rather than indirectly via a gasification and methanol synthesis approach, provides a significant contribution to the goal of providing clean alternatives to the use of fossil fuels as a source for vehicle fuel. By way of example, the present invention can be applied to convert glycerol produced from biomass- derived biodiesel into methanol, which can in turn be used in the production of biodiesel.

Whilst the conditions of the method of the present invention are such as to provide a pathway to direct methanol synthesis, and thereby avoid gasification to form synthesis gas, in some embodiments gas phase by-products may be observed. In the case of by-products comprising hydrogen or carbon monoxide, these can be collected and subsequently converted into methanol, for example using a conventional methanol synthesis reaction.

Preferably the oxygenated hydrocarbon is glycerol. However, other oxygenated hydrocarbons, for example ethylene glycol, can also be the starting material for the method of the present invention. A preferred group of oxygenated hydrocarbons is C_2-IO oxygenated hydrocarbons (i.e. oxygenated hydrocarbons containing 2 to 10 carbon atoms), preferably C_2-5 oxygenated hydrocarbons. Preferably the oxygenxarbon ratio is in the range 0.5:1 to 2:1 , suitably about 1 :1. 5

Suitably the reaction temperature is at least 400^°C. The present inventors have found that better conversion and/or better selectivity for methanol can be achieved at temperatures of at least 400⁰C. Suitably, the reaction temperature is at least 410⁰C, preferably at least 420⁰C, more preferably at least 430^°C, more preferably at least

10 435°C and most preferably at least 440⁰C. An upper limit of about 500⁰C is preferred, more preferably about 490⁰C, more preferably about 480⁰C, more preferably about 470⁰C and most preferably about 460⁰C. A particularly preferred range is 440⁰C to 460⁰C, especially 445°C to 455°C. An especially preferred temperature is about 450⁰C.

15

The catalyst may be any Group VIIIB catalyst, suitably containing at least one of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt. Preferably the catalyst is selected from Ru and Pt. Suitably the catalyst comprises Ru. Thus, whilst any Group VIIIB metal may facilitate the direct methanol synthesis pathway, Ru has been found by experimentation to be

20 the most active, and provides the best conversion and/or selectivity for methanol.

As discussed above, the direct production of methanol represents a new pathway and, without wishing to be bound by theory, the present inventors believe that only a single catalyst is required in order to access that pathway. Thus, preferably the

25 catalyst comprises only one Group VIIIB metal. Suitably, the only Group VIIIB metal in the catalyst is Ru. More generally, preferably the catalyst comprises and suitably consists of a single metal selected from the Group VIIIB metals above. That is, preferably only one catalyst is used. It is particularly preferred that Ru is the sole catalyst.

30

Whilst some restrictions on the type and number of the Group VIIIB metal in the catalyst are preferred, the catalyst may comprise other metals, for example as a mixture or alloy. Examples of such other metals are Cu, Zn, Cr, Mo, V, Ti, Mn, Sn and Bi. It is preferred that the catalyst is a supported catalyst. Preferred supports are selected from silica, alumina, zirconia, titania, ceria, magnesium oxide, carbon (including microporous carbon and activated carbon), silica-alumina (including alumin-silicates such as zeolites), silicon carbide, boron nitride and mixtures thereof. A particularly preferred support is carbon, especially microporous carbon.

A particularly preferred combination of metal and support is Ru on carbon (Ru/C), especially Ru on microporous carbon.

The support, if present, can take many forms, for example powder or bead.

Suitably the metal is present on the support in an amount of 0.5 wt% to 20wt% based on total weight of the catalyst, more preferably 2wt% to 10wt%, more preferably 2wt% to 8wt%, more preferably 2wt% to 6wt% and even more preferably 2wt% to 5.5wt%. Particularly preferred loadings are selected from 2wt% to 3wt% and 4.5wt% to 5.5wt%. Examples of preferred loadings include about 2.7wt%, about 4.7wt% and about 5wt%.

Preferably the catalyst is provided in a single-bed reactor. As discussed above, suitably there is no need for multiple catalysts in order to access the direct methanol synthesis. Accordingly, multiple-bed reactors are typically not required.

The present inventors have found that in embodiments, control of the molar ratio of water: oxygenated hydrocarbon can assist in optimising conversion and/or selectivity for methanol. Preferably the molar ratio of wateroxygenated hydrocarbon is at least 3:1 , and more preferably at least 4:1. In addition to contributing to the desired direct methanol synthesis reaction pathway, a further advantage of using a molar ratio of at least 3:1 is that the additional water can assist in reducing the viscosity of the oxygenated hydrocarbon, which makes it easier to feed into the reactor. Another advantage of providing a molar ratio of at least 3:1 is that it favours de-coking. Preferably the molar ratio is no more than 20:1 , more preferably no more than 15:1 , more preferably no more than 12:1, more preferably no more than 10:1 and most preferably no more than 8:1. A particularly preferred range is 3:1 to 20:1 , more preferably 3:1 to 12:1 , more preferably 3:1 to 15:1 , more preferably 3:1 to 10:1 , and most preferably about 3: 1 to 8: 1. An example is about 5: 1. Suitably the oxygenated hydrocarbon and water are pre-heated to a temperature in the range O⁰C to 100⁰C below the reaction temperature. It is preferred that the oxygenated hydrocarbon and water are pre-heated to within 100°C of the reaction temperature.

In particular, it is preferred that the oxygenated hydrocarbon and water are preheated to a temperature greater than the boiling point of the oxygenated hydrocarbon. Suitably preheating occurs at a temperature at least 10⁰C, preferably at least 25°C and most preferably at least 50⁰C above the boiling point of the oxygenated hydrocarbon. Thus, for example, in the case of glycerol, which has a boiling point of 290⁰C, it is preferred that preheating occurs at a temperature in excess of 290⁰C, suitably at least 300⁰C and more preferably at least 350⁰C. This assists in ensuring that the liquid feeds are converted to gases prior to reaction. In addition, it may assist in avoiding a rapid temperature drop in the reactor.

Preferably the oxygenated hydrocarbon and water are delivered to the catalyst in a carrier gas, which carrier gas comprises Ar, He or N₂. N₂ is particularly preferred.

Preferably the reaction occurs at a pressure in the range 1 to 8 bars, more preferably in the range 1 to 5 bars. A particularly preferred example is about 4 bars. By selecting such a pressure suitably the pressure drop in the reaction bed can be compensated for.

Suitably the methanol product is condensed in a liquid-gas separator. Preferably the temperature in the liquid-gas separator is 0⁰C or less, for example about -5°C.

In embodiments, the total conversion of the oxygenated hydrocarbon is at least 65%.

In embodiments, at least 35% of the oxygenated hydrocarbon is converted to liquid phase products, preferably at least 40%.

In embodiments the selectivity for methanol in the liquid-phase product is at least 50%, preferably at least 60%.

Suitably the reaction is carried out in a reactor comprising a pre-heater and a reactor, wherein the reactor is a single bed reactor. Preferably the oxygenated hydrocarbon is derived from biomass, suitably a byproduct of biodiesel production. Thus, the present invention provides a way of utilising a by-product from the increasingly important biodiesel production process. As noted above, if in embodiments hydrogen and carbon monoxide are produced as by-products then they can be converted to methanol using conventional techniques and then utilised in the biodiesel production method.

Suitably the methanol produced by the method of the present invention is separated from the other reaction products. If appropriate, the methanol is purified.

In a further aspect, the present invention provides a use of a Group VIIIB catalyst at a temperature of at least 380⁰C in a method of reforming an oxygenated hydrocarbon.

In a further aspect, the present invention provides methanol obtained by the method of the first aspect.

Any one of the aspects of the present invention may be combined with any one or more of the other aspects. Furthermore, any of the optional or preferred features of any one of the aspects may apply to any of the other aspects.

Detailed Description of Embodiments

Embodiments of the present invention will now be described with reference to the accompanying drawing, in which:

Figure 1 shows a schematic of the apparatus used to conduct the experiments reported herein.

Reactor

As shown in Figure 1 , the apparatus used to demonstrate the direct synthesis of methanol from glycerol comprises a % inch tubular reactor system 2. The two zone reactor includes a pre-heating zone 4 and reaction zone 6. The preheating zone temperature is kept at 400 ⁰C by heater 7, which is much higher than glycerol boiling point of 290 ⁰C. The reaction temperature is in the range of 400 to 500 ⁰C and pressure is from 1 to 5 bars. A mixture of glycerol and water is supplied to the pre-heating zone 4 via liquid supply line 8 by HPLC pump. Nitrogen is used as carrier gas and delivered to the glycerol/water mixture via nitrogen supply line 10. To ensure efficient and consistent vapourisation of the liquid mixture, the preheating zone is packed with silicon carbide 12. The silicon carbide is sandwiched between two plugs of quartz wool 14.

The pre-heated glycerol/water mixture passes into the reactor 6, which is held at the desired temperature by a heater 16.

The tubular reactor 6 comprises a single catalyst bed 18 sandwiched between two plugs of quartz wool 20.

The exit stream from the reactor is cooled down in a liquid-gas separator 22 by using a refrigerated circulator 24, in which ethylene glycol is used as the cooling medium. The temperature of refrigerator circulator 24 is kept at -5 ⁰C to ensure all methanol and heavy components are condensed in the separator 22.

Liquid samples are analyzed using a Shimadzu GC 2014 with a flame ionization detector. Gas products from the separator 22 are introduced into an Agilent GC890N with a thermal conductivity detector to determine hydrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene and propane content.

Catalysts

Whilst other Group VIIIB catalysts can be used, ruthenium has been found to be particularly effective, particularly on carbon supports and especially microporous carbon supports. Indeed Ru on carbon has been found to be very active for direct methanol production from glycerol reforming.

The catalysts used in the present examples are made as follows:

Catalyst A: A powdery activated carbon commercially known as SAE SUPER, purchased from NORIT (Norit Singapore Pte. Ltd.), is used as the support. 0.50Og of carbon support is impregnated with 2 mL of aqueous solution containing 0.050 g of RuCI₃ XH₂O (98%, Aldrich), followed by evaporation and drying at 150 ⁰C for 3 hours. The solid composite is then treated at 900 ⁰C for 2 hours under purified nitrogen (99.999%) atmosphere, during which Ru species are thermally reduced to Ru nanoparticles. Ru loading is calculated as 4.7 wt%. Catalyst B: 0.500 g of activated carbon SAE SUPER is impregnated with 2 ml. of aqueous solution containing 0.030 g of RuCI₃ XH₂O and 0.102 g sucrose, followed by evaporation and drying at 150 ⁰C for 3 hours. The solid composite is then treated at 5 900 ⁰C for 2 hours under purified nitrogen atmosphere. Ru loading is calculated as 2.7 wt%.

Catalyst C: 0.500 g of home-made microporous carbon, which is synthesized using zeolite as template and furfuryl alcohol as carbon precursor is impregnated with 20 mL of aqueous solution containing 0.050 g of RuCI₃ XH₂O, followed by evaporation and drying at 150 ⁰C for 3 hours. The solid composite is then treated at 900 ⁰C for 2 hours under purified nitrogen atmosphere. Ru loading is calculated as 5.0 wt%.

The microporous carbon support in this case is made as follows: Zeolite NH₄Y5 commercially known as CBV300 with a SiO₂/AI₂O₃ of 5.1 , is purchased from Zeolyst International Company (PA, USA) and used as received without further treatment. Furfuryl alcohol (FA, 98%, ACROS ORGANICS, USA) is employed as the carbon precursor. The process of preparation includes three steps. Step 1 is to impregnate zeolite NH₄Y with FA. Before impregnation, NH₄Y is dried at 200⁰C for 4 h in a flask0 and cooled down to room temperature in nitrogen atmosphere. Then, FA is added to the flask (4 ml of FA to 1 g of zeolite NH₄Y). After stirring at room temperature for 72 h, the solid is filtrated off, washed with mesitylene (P98%, Fluka) to remove residual FA, and air-dried. The solid collected after Step 1 is heated to 900⁰C in a quartz tube under N₂ (99.999%) flow to carbonize FA. After 4 h, the tube is cooled down to room5 temperature under N₂ flow. The solid zeolite/carbon composite after Step 2 is dissolved in a large amount of 46% aqueous HF solution at room temperature for 24 h. The black solid which is filtered, washed with hot deionized water five times, and dried at 150⁰C overnight, is used as the support of Catalyst C. 0 The above methods can of course be adapted to make catalysts comprising other Group VIIIB catalysts.

Example 1

Catalyst A: 4.7% Ru on active carbon. 5

Reactant feed: A 5:1 molar ratio of wateπglycerol is supplied to the reactor at a flow rate of 0.05 ml/min, with N₂ as carrier gas at a flow rate of 50 ml/min. Reaction conditions: 0.1 g catalyst A is used. Reaction temperature is 450 ⁰C and the pre-heating zone temperature is 400 ⁰C. The reactor pressure is about 4 bars.

Results: total glycerol conversion is 94% and 55% of glycerol converted to gaseous products such as CO, CO₂, CH₄, C₂H₆ and C₂H₄. The selectivities (%) of gas and liquid phase products are listed in table! .

Table 1. Selectivities of roducts from Gl cerol reformin on catal st A

From table 1 , it can be seen that methanol is the dominant product in the liquid phase. The selectivity of methanol in liquid phase is 63%. This means that 0.22 mole of methanol is produced for each mole of glycerol.

Example 2

Catalyst A: 4.7% Ru on active carbon (same catalyst as example 1).

Reactant feed: A 5:1 molar ratio of waterethylene glycol (EG) is supplied to the reactor at a flow rate of 0.1 ml/min.

Reaction conditions: Same as example 1. Results: total EG conversion is 70% and 33% of EG converted to gaseous products. The selectivities (%) of gas and liquid phase products are listed in table 2.

Table 2. Selectivities of roducts from Eth lene Gl col reformin on catal st A

More methanol is produced from ethylene glycol reforming than glycerol reforming on catalyst A, though ethylene glycol conversion is lower than glycerol conversion under same reaction conditions. The selectivity of methanol in the liquid phase is as high as 94%.

Example 3

Catalyst B: 2.7% Ru on active carbon.

Reactant feed: Same as example 1.

Reaction conditions: Same as example 1.

Results: total glycerol conversion is 100% and 70% of glycerol is converted to gaseous products. The selectivities (%) of gas and liquid phase products are listed in table 3. Table 3. Selectivities of roducts from l cerol reformin on catal st B

Compared with example 1 , methanol selectivity in the liquid phase is almost same, although the Ru loading of 2.7% in this example is much lower than 4.7% of catalyst A in example 1. Catalyst B results in more acetaldehyde production than catalyst A in example 1.

Example 4

Catalyst C: 5.0% Ru on home-made microporous carbon.

Reactant feed: Same as example 1.

Reaction conditions: Same as example 1.

Results: total glycerol conversion is 75% and 36% of glycerol converted to gaseous products. The selectivities (%) of gas and liquid phase products are listed in table 4. Table 4. Selectivities of roducts from l cerol reformin on catal st C

Compared with results in example 1 and 3, catalyst C gives significantly higher methanol selectivity from glycerol reforming, though glycerol conversion is lower. The selectivity of methanol in liquid phase almost reaches 80%. 0.32 mole of methanol is produced for each mole of fed glycerol in this example.

In conclusion, embodiments of the present invention provide a new pathway to produce methanol directly from oxygenated hydrocarbon reforming, particularly glycerol.

Embodiments of the present invention therefore provide a method b which glycerol, the major by-product of biodiesel production, can be recycled.

A principal advantage of embodiments of the present invention is that because methanol is directly produced as a major product from oxygenated hydrocarbon reforming, there is a significantly higher economic, environmental and energy efficiency as compared to the conventional two-step method of producing synthesis gas first then making methanol using the synthesis gas. Another advantage demonstrated by embodiments of the present invention is that the oxygenated hydrocarbon reactants can be produced from renewable sources, such as biomass.

Another advantage of embodiments of the present invention is that it functions at comparatively low temperatures and pressures.

Claims

Claims:

1. A method of producing methanol by oxygenated hydrocarbon reforming, the method comprising the step of: contacting the oxygenated hydrocarbon and water

5 with a Group VIIIB catalyst at a reaction temperature of at least 380⁰C, to yield methanol.

2. A method according to claim 1 , wherein the oxygenated hydrocarbon is glycerol.

10

3. A method according to claim 1 or claim 2, wherein the reaction temperature is at least 400^°C.

4. A method according to claim 3, wherein the reaction temperature is at least 15 425^°C.

5. A method according to claim 4, wherein the reaction temperature is about 450^°C.

20 6. A method according to any one of the preceding claims, wherein the catalyst comprises Ru.

7. A method according to any one of the preceding claims, wherein the catalyst comprises only one Group VIIIB metal.

25

8. A method according to any one of the preceding claims, wherein the catalyst is a supported catalyst.

9. A method according to claim 8, wherein the support is a carbon support. 30

10. A method according to claim 8 or claim 9, wherein the metal is present on the support in an amount of 0.5wt% to 20wt% based on total weight of the catalyst.

11. A method according to any one of the preceding claims, wherein the catalyst 35 is Ru/C.

12. A method according to any one of the preceding claims, wherein the molar ratio of water: oxygenated hydrocarbon is in the range 3:1 to 20:1.

13. A method according to claim 12, wherein the molar ratio is in the range 3:1 to 5 12:1.

14. A method according to any one of the preceding claims, wherein the oxygenated hydrocarbon and water are pre-heated to a temperature in the range 0⁰C to 100^°C below the reaction temperature.

10

15. A method according to any one of the preceding claims, wherein the oxygenated hydrocarbon and water are preheated to a temperature greater than the boiling point of the oxygenated hydrocarbon.

15 16. A method according to any one of the preceding claims, wherein the oxygenated hydrocarbon and water are delivered to the catalyst in a carrier gas, which carrier gas comprises He, Ar or N₂.

17. A method according to any one of the preceding claims, wherein the reaction 20 occurs at a pressure in the range 1 to 8 bars.

18. A method according to claim 17, wherein the pressure is in the range 1 to 5 bars.

25 19. A method according to any one of the preceding claims, wherein the methanol product is condensed in a liquid-gas separator.

20. A method according to any one of the preceding claims wherein the total conversion of the oxygenated hydrocarbon is at least 65%.

30

21. A method according to any one of the preceding claims, wherein at least 35% of the oxygenated hydrocarbon is converted to liquid phase products.

22. A method according to any one of the preceding claims, wherein the 35 selectivity for methanol in the liquid-phase product is at least 50%.

23. A method according to any one of the preceding claims, wherein the reaction is carried out in a reactor comprising a pre-heater and a reactor, wherein the reactor is a single bed reactor.

24. A method according to any one of the preceding claims, wherein the oxygenated hydrocarbon is derived from biomass.

25. A method according to any one of the preceding claims, wherein the oxygenated hydrocarbon is a by-product of biodiesel production.

26. Use of a Group VIIIB catalyst at a temperature of at least 380⁰C in a method of reforming an oxygenated hydrocarbon to form methanol.

27. Use of Ru/C catalyst at a temperature of at least 380⁰C in a method of reforming an oxygenated hydrocarbon to form methanol.

28. Use according to claim 26 or claim 27, wherein the temperature is at least 400⁰C.