NL2006535C2 - Method for the manufacture of methanol. - Google Patents
Method for the manufacture of methanol. Download PDFInfo
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- NL2006535C2 NL2006535C2 NL2006535A NL2006535A NL2006535C2 NL 2006535 C2 NL2006535 C2 NL 2006535C2 NL 2006535 A NL2006535 A NL 2006535A NL 2006535 A NL2006535 A NL 2006535A NL 2006535 C2 NL2006535 C2 NL 2006535C2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Description
METHOD FOR THE MANUFACTURE OF METHANOL
The present invention relates to a method for the manufacture of methanol.
5 Methanol is also designated as methyl alcohol or hydroymethane, and by common terms such as wood alcohol, wood naphtha or wood spirit, and has the chemical formula CH3OH. Methanol is commonly abbreviated by MeOH.
As a chemical product, methanol has received a lot of 10 interest due to its importance for chemical industry.
Further, it has high potential as clean and renewable energy carrier/fuel. A huge advantage over H2 as a fuel is that the liquid can be transported using the existing fuel supply infrastructure with only minor adaptations. The literature 15 suggests that methanol can be a future source of energy supply for sustainable development.
Besides energy applications, it can be used as base chemical in the synthesis of formaldehyde, acetic acid, ethanoic acid, ethanol, ethanoate, dimethylether and a wide 20 variety of other products, e.g. polymers, paints, adhesives, construction materials, synthetic chemicals, pharmaceuticals, etc. Building blocks in the synthesis of synthetic hydrocarbons, such as ethylene and propylene, can be produced from methanol using catalytic reactions.
25 Methanol is mostly produced from synthesis gas (or syngas). Syngas comprises carbon oxides, such as CO and/or CO2, and hydrogen (H2) , but it may also comprise CH4 and/or N2. Some other constituents may also be present in the gaseous mixture.
30 Syngas is produced from methane, coal or biomass. Three methods are known to commercially produce syngas from methane. The first method is steam-methane reforming (or SMR), a process carried out at moderate pressures of up to 2 40 bar and temperatures around 850 °C, in which methane is converted with steam on a catalyst to syngas: CH4 + H20 -5=5- CO + 3 H2 (1)
The second method is partial oxidation of methane (POM) 5 with oxygen: 2 CH4 + 02 ^2 CO + 4 H2 (2)
The two recited methods can also be combined in autothermal reforming (ATR). The ratio of CO and H2 can be adjusted by the water-gas shift reaction to provide the 10 appropriate stoichiometry for methanol synthesis: CO + H20 Ö C02 + H2 (3)
The carbon monoxide and hydrogen in the syngas react on a second catalyst to produce methanol: CO + 2 H2 *=£ CH30H ( 4) 15 When carbon dioxide is present in the gas mixture, hydrogen can be converted within the methanol synthesis reactor, by: C02 + 3 H2 «=* CH3OH + H20 (5)
Both methanol synthesis reaction equations (equations 4 20 and 5) are exothermic and proceed under volume contraction. The reactions are equilibrium reactions and reversible. The equilibrium shifts towards methanol at higher pressures and lower temperatures.
The progress of the reactions is restricted by 25 thermodynamic equilibrium. In commercial methanol synthesis, roughly two reaction conditions can be distinguished. Methanol can be synthesized at high pressure and high temperatures (for example, p > 150 bar and T > 350 °C) as recited in DE 441 433 (High Pressure Process, HP) and at 30 lower temperature and pressures (p < 120 bar and T < 350 °C) as recited in EP 0 790 226 (Low Pressure Process, LP). The LP process arose with the development of more active catalysts and progress in syngas cleaning systems. The LP
3 process is the prevailing process since the end of the 1960s. The process is carried out generally at pressures of 50-100 bar and temperatures of 230 - 300 °C, where the maximum conversion of carbon oxides in the syngas to 5 methanol ranges from 20 to 75%.
The drawbacks of these two processes are that in both cases the syngas conversion is thermodynamically limited to 20 to 75% due to the high temperature for the HP process, and low pressure in the LP process. The low syngas 10 conversion requires a recycle stream to reuse the unconverted syngas. Accordingly, known industrial processes commonly involve a system wherein produced methanol is separated from the unreacted components, which are then returned to the methanol reactor, after being mixed with 15 fresh syngas.
To prevent the building-up of undesirable components in the recycle loop (present in excess and inert components), the syngas requires a strict composition. A so-called stoichiometric ratio (or Sn) can be defined as Sn = (H2-20 CO2)/(CO2+CO) , and its ideal value is 2. Some CO2 is preferred, usually in a range of 2-10 %.
Gas mixtures derived from biomass can have a composition deviating from the 'ideal' Sn value, viz. either a high CO2 content and/or a shortage of H2. This syngas 25 requires additional treatments to arrive at the desired Sn value, for example by addition of supplementary H2 or removal of excess CO2.
The reaction rate in methanol synthesis from hydrogen and carbon monoxide based on elementary reactions with a 30 surface reaction as the rate determining step according to a Langmuir-Hinshelwood mechanism can be presented in simplified form by equation (6):
Rch3oh = k • 6 • pfj2 • pco — (6 ) 4 wherein Rch3oh is the reaction rate of methanol formation, k is a factor that comprises the reaction rate constant and equilibrium constants of elementary equilibrium reactions and 0 is a factor related to the adsorption/desorption 5 behavior of the components, px is the partial pressure of component x, and Keq is the equilibrium constant for eq. 1.
o Pru ou
The term Ph2 ’ Pco ~ can k<e interpreted as the driving force of the reaction, which becomes larger at higher partial pressures of the reactants. If the reaction is at 10 equilibrium the driving force is 0 and no net reaction will take place. The more the gas composition deviates from the equilibrium composition the larger the driving force and effectively the reaction will proceed faster. In the prior art the driving force appears large in the first part of the 15 reactor but decreases significantly when the equilibrium composition is approached, eventually becoming zero.
Additionally, in the methods of the prior art, the formation of by-products during the synthesis of methanol presents the inconvenience that it deactivates the 20 catalysts. Namely, the catalysts used in methanol synthesis from gas mixtures with high CCq concentrations (more than 40% of the total syngas composition) seem to deactivate more rapidly, due to the formation of water causing crystallisation of the components of the catalyst, such as 25 Cu and ZnO, for example.
Further, in known industrial processes, the conversion of syngas reaches conversion rates that require the recycling of the unreacted syngas. Accordingly, known industrial processes involve very commonly a two-part 30 apparatus or a two-reactor system wherein the produced methanol is separated from the unreacted components that are returned to the methanol reactor, together with fresh syngas .
5
Accordingly, there is a continuous need in the prior art to provide better methods for the manufacture of methanol that do not present the above-mentioned drawbacks.
The present invention has for goal, amongst other 5 goals, to provide an improved method for the manufacture of methanol not presenting these drawbacks.
This goal, amongst other goals, is met in the present invention by the method for the manufacture of methanol comprising the steps of: 10 al) providing a gaseous mixture by converting biomass into a gaseous mixture comprising at least one carbon oxide and hydrogen, in water at a pressure of at least 220 bar and a temperature of at least 350°C, and subsequently removing the water; 15 a) introducing in one reactor comprising a catalyst, a gaseous mixture comprising at least one carbon oxide and hydrogen; b) reacting the gaseous mixture at a pressure of at least 150 bar and a temperature of at most 260°C, 20 until the predetermined level of reaction is obtained.
The method of the present invention involves that during the reaction a two phase system is formed comprising a liquid phase rich in methanol and a second phase that is a 25 gas phase comprising amongst others, methanol and the components of the initial gas mixture.
An advantage of the present invention is that due to the formation of a liquid phase in the reactor the driving force for the reaction towards methanol and therefore the 30 reaction rate for methanol formation is significantly higher than in conventional methanol synthesis. Another advantage is that the method does not involve the recycling of the unused syngas or of any unused gaseous mixture (e.g.
6 comprising at least one carbon oxide and/or hydrogen) used as starting material for the manufacture of methanol as high conversion of the limiting reactant (be it H2, CO and/or CO2) is secured. Another advantage is that the present invention 5 provides a method for the manufacture of methanol that can be carried out with any syngas composition, or at least substantially more flexible, or less strict, than conventional methods for the manufacture of methanol. Still other advantages are that the method for the manufacture of 10 methanol according to the present invention can be completed in less time than with conventional methods and the methanol obtained can be high quality methanol. High quality methanol is to be understood by high purity methanol.
Advantageously, the method according to the present 15 invention can be carried out in a reactor chosen from a fixed bed reactor or a fluid bed reactor or a slurry phase reactor. Any steps of the method according to the present invention may or may not be carried out with stirring. Stirring can be of any type. If stirring is carried out, 20 mechanic stirring may be preferred.
In the context of the present invention, a catalyst is a reagent that participates in the chemical reaction, but is not consumed by the reaction itself. The catalyst used in the method of the present invention, can be any commercially 25 known catalyst, such as a catalyst comprising copper, or copper, zinc oxide, or copper zinc oxide and alumina or a catalyst comprising chrome oxide and zinc oxide. The catalyst can advantageously be chosen from a metallic oxide, a metallic hydride, or a metallic oxysalt comprising at 30 least one of the metals chosen from the group Al, Cu, Cr,
Cs, Fe, Ir, La, Mo, Mn, Ni, Pd, Rh, Si, Sm, Ti, Zn.
7
In the context of the present invention, a metallic oxide is a metallic salt wherein the oxidized metal is the cation and the oxide (02~) is the anion.
In the context of the present invention, a metallic 5 hydride is a salt wherein the oxidized metal is the cation and the hydride in the anion of hydrogen, H-, or a compound in which one or more hydrogen centers have nucleophilic, reducing, or basic properties. In compounds that are regarded as hydrides, hydrogen is bonded to a more 10 electropositive element or group. Compounds containing metal or metalloid bonds to hydrogen are often referred to as hydrides, even though these hydrogen centers can have a protic character.
In the context of the present invention, a metallic 15 oxysalt is such as a metallic salt wherein the cation is the oxidized metal and the anion is chosen from the group hydrogen carbonate (HCCh-) , carbonate (CCh2-) , dihydogenophosphate (IhPCh-) , hydrogenophosphate (HPCh2-) , phosphate (HPC>43~), hydrogenosulfate (HSCh”) , sulfate (SC>42~). 20 Step b) of the method according to the present invention is carried out under pressure. The pressure is advantageously at least 150 bar, more advantageously at least 170 bar, most advantageously at least 180 bar. The pressure as such may be as high as necessary and may not 25 have to be limited to a particular maximum. The pressure may advantageously be at most 500 bar. Excellent results have been obtained at a pressure between 200 bar and 250 bar.
Step b) is carried out at a temperature of at most 260°C. Advantageously, the temperature is at most 240°C, 30 more advantageously 225°C. Typically, step b) of the method of the present invention is carried out between 180°C and 220 °C.
8
The predetermined level of reaction in step b) of the method according to the present invention, defines the completion of the conversion of hydrogen and the at least one carbon oxide in the gaseous mixture. It is to be 5 understood as the moment in time, wherein the desired yield of conversion into methanol is achieved, such as at least 80%, at least 85%, at least 90%, at least 95%, 100%. Accordingly, the method according to the present invention comprises performing the reaction until the predetermined 10 level of conversion is reached, then part of the methanol condenses in-situ and it can be further separated from the gas mixture, or conveyed directly to a method using methanol as solvent or as reactant.
According to the method of the present invention, the 15 pressure in step b) is in the range of 150 bar to 500 bar, preferably 160 bar to 300 bar, more preferably 170 bar to 250 bar.
The pressure in step b), is in the range of 150 bar to 500 bar, may be any value within this range. Such values can 20 be such as 150 bar, 160 bar, 170 bar, 180 bar, 190 bar, 200 bar, 210 bar, 220 bar, 230 bar, 240 bar, 250 bar, 260 bar, 270 bar, 280 bar, 290 bar, 300 bar, 310 bar, 320 bar, 330 bar, 340bar, 350 bar, 360 bar, 370 bar, 380 bar, 390 bar, 400 bar, 410 bar, 420 bar, 430 bar, 440 bar, 450 bar, 460 25 bar, 470 bar, 480 bar, 490 bar, 500 bar.
According to the method of the present invention, the temperature in step b) is in the range of 150°C to 260°C, preferably 160°C to 225°C, more preferably 170°C to 220°C.
The temperature in step b) may be of any value within 30 this range. Such values can be such as 150°C, 155°C, 160°C, 165°C, 16 0 °C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195 °C, 200 °C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235 °C, 240 °C, 245°C, 250°C, 255°C, 260°C.
9
According to the present invention, the gaseous mixture of step a) comprises at least one carbon oxide and hydrogen. The term "at least one carbon oxide" is to be understood as at least one sort of carbon oxide, such as carbon monoxide 5 or carbon dioxide. Accordingly, the composition of the gaseous mixture, or syngas, is CO and/or CO2, and H2. Additionally, the gaseous mixture may comprise N2 and/or CH4. Typically, when the gaseous mixture, or syngas, is obtained by a method prior to the method for the manufacture of 10 methanol according to the present invention, the gaseous mixture may be prepared in water at conditions wherein the water is in the supercritical phase.
The gaseous mixture may comprise about 20%(+/- 10%) CO, 20% CO2( + /- 20%), 50% ( + /- 25%) H2. Additionally, the syngas 15 may contain: 10% (+/- 5%) N2 and/or 10% (+/- 5%) CH4, and/or 10% (+/- 5%) higher hydrocarbons.
According to the method of the present invention, the catalyst in step a) is a metallic oxide catalyst comprising at least one oxide of the metals chosen from the group Al, 20 Cu, Cr, Cs, Fe, Ir, La, Mo, Mn, Ni, Pd, Rh, Si, Sm, Ti, Zn.
The catalyst in step a) is a metallic oxide catalyst comprising at least one oxide of the metals chosen from the group Al, Cu, Cr, Cs, Fe, Ir, La, Mo, Mn, Ni, Pd, Rh, Si,
Sm, Ti, Zn. It can be composed of at least one oxide of the 25 metal, such as the oxide of one metal, the oxide of two metals, the oxide of three metals, the oxide of four metals, the oxide of five metals or the oxide of six metals. Any combination or particular type of oxides is suitable as a catalyst. In the method of the present invention, the 30 catalyst used can be any known catalyst for the manufacture of methanol.
Additionally, the catalyst may contain a promoter. A promoter is a component increasing the activity and 10 selectivity of the catalyst. The promoter is advantageously chosen from alkaline-earth and rare-earth metals. Non-metallic bases may also be suitable promoters.
According to the present invention, the catalyst 5 comprises a stabilizing agent chosen from the group AI2O3, Ce02, Cr203, La205, Mn02, Mo02, Si02, Ti02, V205, W02, Zr02. The stabilizing agent is an agent stabilizing the catalyst. It is to be understood as a support for the catalyst, it does not in any case act as catalyst.
10 According to a preferred embodiment of the present invention, the stabilizing agent is present in an amount of not more than 30 % by mass of the catalyst, advantageously not more than 25% by mass of the catalyst, advantageously not more than 20% by mass of the catalyst.
15 According to the method of the present invention, no recycling of unreacted gaseous mixture is effectuated at any stage of the method.
Surprisingly, when carrying out the method of the present invention, two phases, of which a liquid phase 20 (comprising liquid methanol) and a gas phase (comprising methanol and components of the initial gas mixture), are formed in step b) of the present invention. Due to condensation of (at least part of) the methanol, the equilibrium composition shifts towards methanol and will 25 only be reached for very low hydrogen and carbon monoxide concentrations. The driving force towards methanol will remain much higher over the reactor bed compared to the prior art. Accordingly, no recycling of the syngas is necessary in the method according to the present invention. 30 When condensing "at least part of the methanol", it is here to be understood as "any quantity of" methanol is condensed.
The liquid phase that is formed in the reactor is isolated. The term "isolated" is to be understood that the 11 liquid phase, comprising methanol as main component, is withdrawn from the reactor. Methanol is separated from the remaining gas phase after step b). This can be done by different separation techniques including, such as, cooling, 5 adsorption, and extraction. Optionally, both liquid phase products (or liquid methanol) may be further purified, or treated to obtain more pure methanol. The methanol is obtained at the end of the method in a liquid form. Due to the formation of the methanol in the liquid form, the method 10 of the present provides methanol which can be of a surprisingly high purity. Additionally, for further utilization of the methanol, or for specific applications, the methanol obtained may be submitted to subsequent treatments. However, the methanol obtained according to the 15 present invention may also be used without further treatments. Further treatment may be a purification step, for example by distillation, and/or by phase separation, and/or sedimentation and/or filtration and/or chromatography .
20 Accordingly the present invention, the method for the manufacture of methanol may comprise a step al) that is carried out prior to step a) comprising: al) providing the gaseous mixture by converting biomass into the gaseous mixture comprising at least one carbon 25 oxide and hydrogen, in water at a pressure of at least 200 bar and a temperature of at least 350°C, and subsequently removing the water.
Accordingly, in the process of the present invention, the hydrogenation reactions of the at least one carbon oxide 30 proceed under volume contraction and high pressure methanol synthesis accordingly requires syngas, or a gaseous mixture, as starting material, that is preferably produced at high pressure. Accordingly, the method for the manufacture of 12 methanol according to the present invention, comprises a step al), before step a), that allows the syngas to be directly produced at a suitable pressure for carrying out the method for the manufacture of methanol according to the 5 present invention. Accordingly, the use of the syngas produced from biomass at high pressure, is favourable to the method for manufacture of methanol according to the present invention .
Industrially, strict limitations of the composition of 10 the synthesis gas may be necessary to prevent the build-up of inert components and unconverted components in the recycle loops. However, syngas provided from any source of biomass according to the present invention may be of any composition which is suitable for the production of 15 methanol. The biomass can originate from any source. When the syngas is prepared at high pressure, it can directly be used in the method for the manufacture of methanol, avoiding removal of inerts, before or during the manufacture of methanol. Another advantage of the present invention, is 20 that due to the high conversion rate of the at least one carbon oxide and hydrogen into methanol in the method of the present invention, the composition of the gas mixture is not strictly limited. The composition of the syngas suitable for carrying out the manufacture of methanol, is advantageously 25 not limiting compared to the prior art.
According to a preferred embodiment of the present invention, the biomass converted in step al) is a vegetal material.
The biomass can come from a vegetal material or vegetal 30 sources, such as starches and bio-diesel from pure plant oils, but also from bio-ethanol from sugar sources, or glycerol from biodiesel production. The biomass can be 13 derived from any material containing lignitic and/or hemi-cellulosic and/or cellulosic materials.
The pressure in step al) is in the range of 200 bar to 400 bar and can take any value within this range. Such value 5 can be such as, but not limited to 250 bar, 255 bar, 260 bar, 265 bar, 270 bar, 275 bar, 280 bar, 285 bar, 290 bar, 295 bar, 300 bar.
Advantageously, the pressure in step al) is below 400 bar. Advantageously, the pressure in step al) is above 220 10 bar.
According to another preferred embodiment of the present invention, the pressure in step al) is in the range of 220 bar to 300 bar.
Yet in another preferred embodiment of the present 15 invention, the temperature in step al) is in the range of 350°C to 700°C.
The temperature in step al) is in the range of 350°C to 700°C and can take any value within this range. Such value can be such as 350°C, 355°C, 360°C, 365°C, 370°C, 375°C, 20 380°C, 385°C, 390°C, 395°C, 400°C, 405°C, 410°C, 415°C, 42 00 C, 425 °C, 430 °C, 435°C, 440°C, 445°C, 450°C, 455°C, 46 0 °C, 46 50 C, 470 °C, 475°C, 480°C, 485°C, 490°C, 495°C, 500°C, 505 °C, 510 °C, 515°C, 520°C, 525°C, 530°C, 535°C, 540 °C, 545 °C, 550 °C, 555°C, 560°C, 565°C, 570°C, 575°C, 25 580°C, 585 °C, 590°C, 595°C, 600°C, 605°C, 610°C, 615°C, 620°C, 625°C, 630 °C, 635°C, 640°C, 645°C, 650°C, 655°C, 660°C, 665°C, 670°C, 675°C, 680°C, 685°C, 690°C, 695°C, 700°C.
Advantageously, the temperature in step al) is above 30 350°C, more advantageously above 400°C, most advantageously above 550°C.
The methanol manufactured according to the present invention can be used for the manufacture of other 14 components, such as hydrocarbons. The methanol obtained can be further processed in order to manufacture carboxylic hydrocarbons and/or other hydroxyhydrocarbons.
According to the present invention, the methanol 5 manufactured can be further processed in order to manufacture carboxylic hydrocarbons and/or other hydroxyhydrocarbons. These further methods include, for example, contacting the methanol with carbon monoxide, also designated as a carbonylation reaction, to prepare and 10 obtain ethanoic acid (CH3COOH). The ethanoic acid can further be contacted with hydrogen, also designated as a hydrogenation reaction, to produce ethanol (CH3CH2OH) and/or ethyl ethanoate. These further steps are carried out in the known reaction conditions for carbonylation of methanol.
15 Additionally, they may involve the presence of a suitable catalyst, such as one or more of the catalysts selected for the manufacture of methanol according to the present invention, or a promoter such as described within the context of the present invention.
20 The present invention is illustrated by the present examples and figures. The present examples do not limit the invention in any way.
Figure 1 Picture of the view cell reactor.
The stirrer (visible inside the 25 view cell) contains a small basket which spins and can contain catalyst
Figure 2 Schematic flowsheet of the view cell reactor.
30 Figure 3 The formation of liquid methanol in the view cell. The actual size of the image displayed in the picture is approximately 2 cm. The black 15 object in the right upper part of the picture is the basket. The left grayish bottom part is the wall of the view cell. The somewhat 5 transparent phase is the liquid phase. The reactor is operated in dead end mode. Process conditions: T = 200 °C, P = 200 bar. Feed gas composition: H2 (65 vol%), CO (25 10 vol%), C02 (5 vol%), and CH4 (5 vol%).
Figure 4 Liquid methanol in the view cell.
The width of window in the picture is approximately 2.2 cm. A chain of 15 catalyst is wound around the shaft of propeller shaped stirrer. The surface level of the liquid phase is clearly visible. The reactor is operated in semi batch mode.Process 20 conditions: T = 200 °C, P = 200 bar. Feed gas composition: H2 (65 vol%) , CO (20 vol%), C02 (5 vol%), and CH4 (5 vol%).
25 Examples
Example 1: packed bed experiment (reference) A commercial catalyst (Haldor Topsoe (MK-121) was tested in a packed bed reactor. The catalyst contains Cu as active metal. The catalyst was activated by temperature programmed 30 reduction in N2 gas flow containing 4 vol% H2.
The activity of catalysts was determined by measuring the CO + C02 conversion as a function of the temperature. In this 16 reference experiment carried out at a pressure of 80 bar, a stoichiometric 'ideal' feed gas was used (H2 - 65.7 vol%, CO -23.9 vol%, C02 - 4.8 vol% and N2 - 4.6 vol%) . These gases (H2, CO, C02, CH4, and N2) were supplied by Linde Gas Benelux.
5 It shows that the CO + C02 conversion increases with increasing temperature, reaching a maximum at around 260 °C.
At temperatures below 260 °C the reaction appears too slow to reach complete equilibrium. Accordingly, the reaction is thermodynamically limited.
10
The resulting values for the liquid yield, MeOH production rate and MeOH product purity are shown in Table 1. The liquid yield increases significantly with increasing temperature and at 260 °C the production rate is 4.04 15 g/h/gcat. The liquid product consists of 98 % methanol. The purity of methanol increases with increasing temperature.
Table 1. Performance of commercial catalyst as function of the temperature T Liquid yield MeOH yield MeOH purity (°C) (g/hr / gcat) (g/hr/gcat) (%) 2ÏÏÖ 0.17 0.14 80 230 1.00 0.90 90 260 4.14 4.04 98 20
Reaction conditions: P = 80 bar, <|)v = 250 Nml/min, Vcat = 1 ml, Wtcat = 1.05 g.
Example 2 (according to the present invention) 25 Methanol synthesis was carried out at high pressure and relatively low temperature in a so-called view cell reactor, see Figure 1. The view cell is a reactor system with a transparent sapphire window to allow visual observation of, 17 in the present case, the methanol synthesis. A schematic representation of the set-up is shown in Figure 2.
A feed gas containing H2 - 65 vol%, CO - 25 vol%, C02 - 5 vol%, and CH4 - 5 vol% was pressurized and fed from a storage 5 container to the view cell. The pressure drop in the gas storage container is monitored to calculate the gas feed rate. The view cell exit is closed ('dead end').
The view cell is heated electrically. The view cell holds a small basket containing commercial Haldor Topsoe MK-121 10 catalyst particles. The basket is stirred. Due to volume decrease (contraction) during methanol synthesis, gas can be fed constantly to reactor to keep the pressure constant in the view cell.
Figure 3 shows photographs of the view cell in operation, 15 just in the stage that in-situ liquid methanol is produced at 200 °C and 200 bar.
It can be seen in figure 3 that just below the basket a droplet is formed which slowly elongates and then touches the reactor wall before it laces up and comes loose. In the 20 beginning of the formation of a liquid product the product evaporates almost instantly when it makes contact with the reactor wall. This effect is probably caused by the slightly higher temperature of the reactor wall compared to the catalyst bed. The view cell slowly fills up with up methanol 25 during reaction time. Fig. 4 shows the reactor (now with a chain of catalyst particles), partly filled with methanol.
Example 3 (according to the present invention)
Packed bed experiment 30 When the present invention is carried out in a packed bed reactor, with gaseous mixtures of various compositions, it was shown that higher yields than the chemical equilibrium of the methanol formation, are obtained.
18
Legend of the figures 2 and 4 (1) H2 inlet (2) CO inlet 5 (3) CO2 inlet (4) CH4 inlet (5) model gas inlet (6) gas booster (7) gas storage bomb 10 (8) view cell (9) stirrer (10) to gas chromatograph (11) sample point (12) pressure 15 (13) temperature (14) cooling system (15) flow controls (MFC) (16) flow controls (MFM) (17) sample point 20 (18) catalyst (19) liquid level 19
CLAUSES
1. Method for the manufacture of methanol comprising the steps of : 5 al) providing a gaseous mixture by converting biomass into a gaseous mixture comprising at least one carbon oxide and hydrogen, in water at a pressure of at least 220 bar and a temperature of at least 350°C, and subsequently removing the water; 10 a) introducing in one reactor comprising a catalyst, a gaseous mixture comprising at least one carbon oxide and hydrogen; b) reacting the gaseous mixture at a pressure of at least 150 bar and a temperature of at most 260°C, 15 until the predetermined level of reaction is obtained.
2. Method according to claim 1, wherein the pressure in step b) is in the range of 150 bar to 500 bar, preferably 160 bar of 300 bar, more preferably 170 bar to 250 bar.
20 3. Method according to claim 1 or 2, wherein the temperature in step b) is in the range of 150°C to 260°C, preferably 160°C to 225°C, more preferably 170°C to 220°C.
4. Method according to any one of claims 1 to 3, wherein the gaseous mixture of step a) comprises CO and/or 25 C02.
5. Method according to any one of claims 1 to 4 wherein the catalyst in step a) is a metallic oxide catalyst comprising at least one oxide of the metals chosen from the group Al, Cu, Cr, Cs, Fe, Ir, La, Mo, Mn, Ni, Pd, Rh, Si, 30 Sm, Ti, Zn.
6. Method according to any one of claims 1 to 5, wherein the catalyst comprises a stabilizing agent chosen from the group A1203, Ce02, Cr203, La205, Mn02, Mo02, Si02, Ti02, V205, WO2, Zr02 .
20 7. Method according to claim 6, the stabilizing agent is present in amount of not more than 30% by mass of the catalyst.
8. Method according to any one of claims 1 to 7, 5 wherein no recycling of unreacted gaseous mixture is effectuated at any stage of the method.
9. Method according to any one of claims 1 to 8, wherein part of the methanol is isolated in liquid form.
10. Method according to any one of claims 1 to 9, 10 wherein the biomass is vegetal material.
11. Method according to any one of claims 1 to 10, wherein the pressure in step al) is in the range of 220 bar to 400 bar.
12. Method according to any one of claims 1 to 11, 15 wherein the temperature in step al) is in the range of 350°C to 700°C.
13. Use of the methanol manufactured according to any one of claims 1 to 12, wherein the methanol obtained is further processed in order to manufacture carboxylic 20 hydrocarbons and/or other hydroxyhydrocarbons.
Claims (13)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1366367A (en) * | 1970-11-18 | 1974-09-11 | Basf Ag | Methanol synthesis catalysts |
| US4031123A (en) * | 1975-11-21 | 1977-06-21 | Chem Systems Inc. | Methanol production in a paraffinic medium |
| EP0448019A2 (en) * | 1990-03-19 | 1991-09-25 | Haldor Topsoe A/S | Method of preparing methanol |
| WO2007117590A2 (en) * | 2006-04-05 | 2007-10-18 | Woodland Biofuels Inc. | System and method for converting biomass to ethanol via syngas |
-
2011
- 2011-04-04 NL NL2006535A patent/NL2006535C2/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1366367A (en) * | 1970-11-18 | 1974-09-11 | Basf Ag | Methanol synthesis catalysts |
| US4031123A (en) * | 1975-11-21 | 1977-06-21 | Chem Systems Inc. | Methanol production in a paraffinic medium |
| EP0448019A2 (en) * | 1990-03-19 | 1991-09-25 | Haldor Topsoe A/S | Method of preparing methanol |
| WO2007117590A2 (en) * | 2006-04-05 | 2007-10-18 | Woodland Biofuels Inc. | System and method for converting biomass to ethanol via syngas |
Non-Patent Citations (1)
| Title |
|---|
| W. K. LEWIS ET AL: "Synthesis of Methanol from Carbon Monoxide and Hydrogen", INDUSTRIAL & ENGINEERING CHEMISTRY, vol. 20, no. 3, 1 March 1928 (1928-03-01), pages 285 - 290, XP055010374, ISSN: 0019-7866, DOI: 10.1021/ie50219a021 * |
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