AU2010362092A1

AU2010362092A1 - Method and apparatus for the integrated synthesis of methanol in a plant

Info

Publication number: AU2010362092A1
Application number: AU2010362092A
Authority: AU
Inventors: Roland Meyer-Pittroff
Original assignee: Silicon Fire AG
Current assignee: Silicon Fire AG
Priority date: 2010-10-06
Filing date: 2010-11-10
Publication date: 2013-04-18
Anticipated expiration: 2030-11-10
Also published as: EP2624947A1; EP2624947B1; ES2584532T3; EP2625136A1; AU2010362092B2; WO2012045349A1; AU2010362120A1; WO2012045373A1

Abstract

The present invention concerns a process (called ComFuel process) and apparatus (100) for the cogeneration of electric energy and methanol. The apparatus (100) comprises - a combustion chamber (10) designed for an oxygen-based combustion process. The combustion chamber (10) has a flue gas outlet (11), a hydrocarbon infeed (12), and an oxygen gas infeed (13). - a sequestration facility (20) designed for the separation of carbon dioxide from flue gas. The sequestration facility (20) comprises a carbon dioxide outlet (21). - a reforming plant (30) having a syngas outlet (31), the reforming plant (30) being connected to the carbon dioxide outlet (21) and being designed for carrying out a reforming process which produces syngas comprising carbon monoxide and hydrogen gas. A gaseous hydrocarbon inlet (32) is connected to the reforming plant (30). - a water electrolysis facility (40) suppliable by electric energy (E1). The water electrolysis facility (40) is designed to produce hydrogen gas and oxygen gas. It comprising a hydrogen gas outlet (41) and an oxygen gas outlet (42). - a methanol reactor (50) for synthesizing methanol, the methanol reactor (50) comprising a methanol outlet (51), a feed gas inlet (52) for feeding the syngas and the hydrogen gas obtained from the water electrolysis facility (40) into the methanol reactor (50).

Description

WO 2012/045373 PCT/EP2010/067182 1 Method and apparatus for the integrated synthesis of methanol in a plant [0001] The present invention concerns a method and apparatus for the integrated synthesis of methanol in a plant. [0002] The present invention claims the priority of the international patent application PCT/EP2010/064948, which is currently assigned to the applicant of the present application and which was filed on 6 October 2010. [0003] The hydrogen economy is believed to have the potential to replace essentially the fossil fuel economy. The introduction of the hydrogen economy would also cut carbon dioxide emissions and it would reduce the dependence on fossil fuels. Methanol (CH 3 0H) from hydrogen is regarded to be far more convenient than the very light, reactive and volatile hydrogen. Methanol is at normal conditions a liquid which clean burns and requires only minor modifications to existing fuel-delivery infrastructure and to combustion engines. If the synthesis of methanol would make use of carbon dioxide, the carbon dioxide footprint could be reduced. [0004] There are a number of projects concerning various aspects of the carbon dioxide based methanol synthesis. Experiments have revealed that the catalyzers which are used for synthesizing methanol are very sensitive to impurities. If the carbon dioxide is to be taken from the flue gas of a power plant, there are a number of impurities and contaminants which would have to WO 2012/045373 PCT/EP2010/067182 2 be removed. A typical washing solution, such as an amine-based solution, which is used for the sequestration of carbon dioxide in large scale systems, is not able to provide carbon dioxide in a form which is clean enough for use in a subsequent methanol synthesis reactor. [0005] Currently, most of the worldwide production of methanol of approximately 40 m metric tons per year is derived from natural gas, with the main component methane (CH 4 ). The corresponding production process has two stages: (1) converting the natural gas into syngas (a mixture of primarily carbon monoxide and hydrogen), and (2) the syngas into methanol. The respective process is called "Natural Gas Based Methanol Production". Although these steps have become more efficient over time, step (1) is still a subject of R&D for further improvement. One reason therefore is that this step (1) is regarded to account for more than 60 % of the cost of the methanol production. [0006] An alternative process for the production of methanol is called "Coal Based Methanol Production". In this process coal is used as feedstock for the methanol production. The corresponding process in principle also follows the main steps of the natural gas process. [0007] In general, methane reactions are hard to control and methane is chemically relatively inert. It combines completely with oxygen or other reactants only at relatively high temperatures. The main reactions with methane are: combustion, reforming to syngas, and halogenation. [0008] The reforming, also called fossil fuel reforming, is a method of producing hydrogen or other gaseous products from carbon containing raw materials like natural gas. The steam reforming of natural gas, known as steam methane reforming (SMR), is shown in reaction [1]:

CH

4 + H 2 0 (gaseous) + CO + 3H 2 AH = +206.2 kJ/mol [1] [0009] This reaction [1] is strongly endothermic which means that is consumes heat. The reforming reaction [1] takes place at high temperatures around 1000 0 C, making it slow to start up and requiring costly high temperature WO 2012/045373 PCT/EP2010/067182 3 materials. [00010] The following equation [1.1] shows another endothermic reforming reaction:

CH

4 + CO 2 + 2CO + 2H 2 AH = +247 kJ/mol [1.1] [00011] Note that the compositions or stoichiometries of the syngases of equations [1] and [1.1] are different. The reforming of methane with CO 2 according to equation [1.1] is an endothermic reaction. Reaction [1.1] is also known as CO 2 reforming of CH 4 . In Reaction [1.1] the deactivation of the catalyst by coke formation reserves a challenge in the development of a practical catalyst. [00012] It is a disadvantage that the reforming of fossil fuels, such as methane, does not eliminate carbon dioxide emissions into the atmosphere since any oxygen-consuming combustion of carbon (C) produces CO 2 , according to the following schematic equation: C + 02 + CO 2 AH = -393.8kJ/mol [2] [00013] The oxygen-consuming combustion [2] is exothermic which means that it produces or provides energy in the form of heat. [00014] If this combustion is carried out using air as oxygen carrier, which contains approximately 79 vol.-% nitrogen (N 2 ) and 21 vol.-% oxygen (02), the combustion is prone to producing by-products, especially nitrogen oxides (NOx). It is known in the art to run the combustion process with pure oxygen. In this case pure CO 2 is produced, as illustrated in equation [2]. [00015] It is also known in the art to run a combustion process with an increased oxygen content. The required oxygen can be provided from a water electrolysis, as disclosed in the patent US 5,342,702 with title ,,Synergistic process for the production of carbon dioxide using a cogeneration reactor".

WO 2012/045373 PCT/EP2010/067182 4 [00016] Combustion processes are currently being tested in pilot plants where an air-separation step is carried out to separate nitrogen and oxygen. An oxygen-rich gas is then fed into a combustion zone. It is an advantage of this approach that the combustion is more efficient since it takes place at higher temperatures and produces less flue gas (with less nitrogen). It is, however, a disadvantage that the air-separation plant requires investment and operational costs and energy. [00017] The CO 2 produced in a combustion process has to be separated out if one wants the C0 2 -emission of the respective plant to be reduced by a post processing of the CO 2 . The flue gas containing the CO 2 typically also contains nitrogen, dust, sulfur oxides, water vapour and other constituents or components. Fossil power plants thus require a special sequestration system for separating the CO 2 from the rest of the flue gas constituents or components. The respective washing process currently used consumes quite some energy. This means that a significant proportion of the energy produced by a fossil power plant is to be re-invested in the CO 2 sequestration. The cleaner the combustion process is and the higher the concentration of CO 2 is, the easier and more efficient is the respective C0 2 -capturing process. In this respect it is advantageous to run a combustion process so that it is close to the pure oxygen based combustion of equation [2]. The pure oxygen-based combustion is herein referred to as ,,clean" combustion. [00018] It is desirable that at least some of the required energy for the post processing of CO 2 would come from renewable sources and not from fossil sources because the renewable sources are not limited and climate neutral. [00019] Methanol produced from a smart mixture of renewable and fossil energies would be more climate friendly than fossil methanol. If the methanol would be produced from CO 2 , the overall CO 2 footprint could be reduced. Details of a technology enabling the smart mixture of renewable and fossil energies for the methanol production are disclosed in the international patent application W02010069622A1, currently held by the applicant of the present application. [00020] The above-mentioned patent US 5,342,702 also mentions the WO 2012/045373 PCT/EP2010/067182 5 possibility to produce methanol using some of the CO 2 produced as by-product in a main process which uses a feed stream of organic combustible fuel and hydrogen. [00021] The final energy from renewable sources is in most cases electric energy. For instance wind farms, solar plants and hydropower plants typically generate electric energy. The electric energy could be used to drive auxiliary units of the C0 2 -sequestration facilities, or the electric energy could be used to drive the above-mentioned air-separation. These approaches are, however, not regarded to be very promising. The invention therefore uses a different approach. [00022] In order to efficiently produce methanol, the stoichiometric composition of the reactants has to be proper, as shown in the following equation: CO + 2 H 2 + CH 3 0H (liquid) AH = - 128.2 kJ/mol [3] [00023] The synthesis of 1 mol of CH 3 0H requires 2 mol H 2 and 1 mol CO. [00024] It is known in the art to produce hydrocarbons from hydrogen and

CO

2 . If one would take the CO 2 from a power plant flue gas, the energetic efficiency and the cleaning capability of the sequestration process are essential. [00025] It is known in the art to generate power in combination with the sequestration of C0 2 -emissions. The respective process, disclosed in patent US 6,148,602, with title ,,Solid-fueled power generation system with carbon dioxide sequestration and method therefore", includes the compression of ambient air, the separation of pure oxygen from the ambient air and as a further step the compression of the oxygen separated from the ambient air. After the oxygen has been further compressed, the oxygen is divided into a first oxygen stream and a second oxygen stream. The first oxygen stream and a solid fuel, such as coal, are fed into a solid-fuel gasifier for converting the first oxygen stream and the solid fuel into a combustible gas. The gas is then combusted in the presence of the second oxygen stream.

WO 2012/045373 PCT/EP2010/067182 6 [00026] Another process is disclosed in WO 2008/012039, with title ,,Verfahren zur Reduzierung der C02-Emission fossil befeuerter Kraftwerksanlagen", where hydrogen is obtained electrolytically. [00027] It is also known in the art to generate power by an oxygen-enriched combustion of coal in combination with the C0 2 -based synthesis of methanol. The respective process is disclosed in WO 95/31423 with title ,,Production of methanol". According to this patent application, DC power from a photovoltaic system is used to supply a water electrolysis system. The hydrogen is used for the methanol production. The oxygen may be used to feed the combustion process. Summary of the invention: [00028] According to the invention, one process step is the ,,clean" combustion of a carbon-containing material, such as coal (hard coal, lignite), natural gas, or biomaterials (e.g. biogenic plant materials or other organic materials). It is also conceivable to combust coal together with biomaterials (e.g. hard coal or lignite together with wood chips). The ,,clean" combustion requires the supply of pure oxygen or the supply of an oxygen-containing gas having an oxygen concentration of at least 60%. The corresponding combustion (oxidation) of pure carbon with pure oxygen is described in equation [2]. The ,,clean" combustion process has the advantages that on the one hand the combustion as such is more efficient, if an adequate combustion chamber and combustion system (optionally with flue gas recirculation and/or high-temperature resistant coating, overlay or layer) are used which are designed to correspond with the significant higher combustion temperature (to withstand temperatures between 800 and 1000 0 C). On the other hand, the flue gas contains a higher C0 2 concentration and fewer or less critical contaminants and impurities (for instance no NOx), which makes a subsequent C0 2 -sequestration process more efficient and robust. [00029] According to the invention, a further process step is the conversion of gaseous hydrocarbons (preferably methane) and carbon dioxide into syngas (a WO 2012/045373 PCT/EP2010/067182 7 mixture of primarily carbon monoxide and hydrogen). A reforming process is here used for the conversion of the gaseous hydrocarbons by means of carbon dioxide (cf. reaction [1.1]), despite of the negative assessment of the experts concerning the applicability of this reforming process in industrial scale processes or power plant processes. [00030] In order to optimize the reforming process in respect to the energetic balance and also to the reaction conditions (e.g. to avoid the formation of soot) the primary reforming reaction of methane [1.1] can be combined to a certain extent with the reactions: steam reforming CH 4 + H 2 0 (gaseous) = CO + 3H 2 + 206.2 kJ/mol [1.2] and direct oxidation CH 4 + 0.502 = CO + 2H 2 - 36 kJ/mol [1.3]. [00031] According to the invention, a further process step is the water electrolysis where water is split into hydrogen and oxygen using electric energy, as summarized by the following equation [4]:

H

2 0 = H 2 + 0.502 AH = +286.02 kJ/mol [4]. [00032] In a preferred embodiment of the invention, the electric energy consumed by the water electrolysis is at least to some extent provided from renewable sources. Most preferred is an embodiment where all of the electric energy for the water electrolysis is renewable. Some of the electric energy might be provided by the ,,clean" combustion process, the combustion chamber of which is part of a gas and /or steam power plant where the electric generator is driven by the gas and/or steam turbine. [00033] According to the invention, a further process step is the synthesis of methanol (e.g. in accordance with reaction [3]). This synthesis is carried out using the ideal or close-to-ideal stoichiometric ratio of reactants in a very pure form.

WO 2012/045373 PCT/EP2010/067182 8 [00034] These steps, which so far were regarded as individual steps, according to the present invention form a nearly ideal process matrix for the efficient production of methanol. The expression "matrix" is herein used to emphasize the fact that the above-mentioned process steps are not coupled one after the other in a linear process chain. Instead the processes are intertwined and dependent on each other. [00035] It is a special advantage of this process matrix that the methanol so produced is to some extent renewable and that at the same time it is C0 2 -neutral since CO 2 emissions from a fossil combustion process are ,recycled". [00036] It is a further advantage of the present invention that the oxygen from the electrolysis (cf. reaction [4]) is used in the process matrix in order to feed or drive the "clean" combustion process (reaction [2]) and - if carried out the direct oxidation process (reaction [1.3]). [00037] The inventive process matrix is regarded to be a synergistic process where all reactants are constituents of a stoichiometrically optimized setup. [00038] The inventive process matrix is regarded to be a cogenerating process matrix since it in the first place produces or provides energy (electric energy and/or heat) from the ,clean" combustion of the carbon-containing material (reaction [2]) and - if carried out - from the direct oxidation process (reaction [1.3]), and in form of loss energy from the electrolysis process (reaction [4]) and the synthesis process (reaction [3]). The carbon-containing material used for the ,clean" combustion (reaction [2]) is thus herein called primary energy carrier. The inventive process matrix also provides methanol which at least to some degree is considered renewable. The gaseous hydrocarbons (preferably methane) are employed in order to provide the energy which is required for the reduction of CO 2 . CH 4 is an example for a reducing agent. Other (preferably gaseous) hydrocarbons could be used instead or in addition. [00039] The CO 2 and the gaseous hydrocarbons (preferably methane) together serve as carbon sources for the production of methanol. All of the WO 2012/045373 PCT/EP2010/067182 9 carbon of the CO 2 and the gaseous hydrocarbons (preferably methane) is transformed into CO. The CO is then used to synthesize the methanol. The gaseous hydrocarbons (preferably methane) are herein called secondary energy carrier. It is an advantage of the invention to rather than using CO 2 for synthesizing methanol, the CO 2 is transformed (reduced) in an intermediate step into CO. Impurities of the C0 2 -gas which have not been removed during the sequestration process are thus not introduced into the catalyzer required for the methanol synthesis. The reforming process was found to be more tolerant to impurities than the methanol synthesis. [00040] The present invention relates to an integrated process matrix for producing energy (electric energy and/or heat) and methanol. The term ,,integrated" is herein used to define a process matrix where all four process steps of the matrix are directly connected or linked concerning the material flows and the energy flows (electric energy and/or heat). [00041] All the energies (heats) of the exothermic process steps [2] and [3] can to a large extent be used in the endothermic process steps [1.1] and [4] and to produce electric energy by means of the gas and/or steam turbine power plant cycle. Also, the reaction and/or loss heats from the water electrolysis and the methanol synthesis can be used within the power plant cycle and/or for preheating of reaction gases like the combustion oxygen, the methane and carbon dioxide for the reforming process as well as the syngas and the hydrogen for the synthesis process. Also, loss heats with lower temperatures can be used for re-heating of flue gases and/or heating a C0 2 -sequestration plant and/or a methanol distillation plant which is employed after the methanol reactor. [00042] The integration is also achieved by using the CO 2 of the "clean" combustion process step as reactant of the process step where the CO 2 together with gaseous hydrocarbons is reformed to syngas. In parallel there is the water electrolysis where water is split into hydrogen and oxygen. This hydrogen together with the hydrogen and the carbon monoxide from the reforming syngas are employed in the methanol synthesis process. The oxygen provided by the electrolysis is fed back into the "clean" combustion process [2] and - if carried out - into the direct oxidation process [1.3].

WO 2012/045373 PCT/EP2010/067182 10 [00043] According to the invention, the CO 2 is not regarded to be a waste product. It is re-used or recycled in that it is employed in the reforming process [1.1] together with gaseous hydrocarbons for the production of syngas. [00044] Since the syngas composition containing CO and hydrogen is not ideal for the synthesis of methanol, additional hydrogen is taken from the electrolysis to complement the syngas. [00045] The integrated nature of the inventive process matrix becomes visible if the respective main equations are listed together:

CH

4 + CO 2 + 2CO + 2H 2 [1.1] C + 02 + CO 2 [2] CO + 2H 2 + CH 3 0H [3]

H

2 0 + H 2 + 1/202 [4]. [00046] In equation [1.1] the methane CH 4 is an example for a reducing agent such as a hydrocarbon. The rearranging of these equations leads to the following matrix: C + 02 + CO 2 [2]

CH

4 + CO 2 + 2CO + 2 H 2 [1.1]

H

2 0 + H 2 + 1/2 02 [4] CO + 2H 2 + CH 3 0H [3] [00047] Step [2] is put at the top of this matrix since this is the basic step for producing/providing energy (electric energy and/or heat). Step [3] is put at the bottom since in accordance with the present invention this process consumes intermediate products from steps [1.1] and [4]. [00048] In the next step these equations are written in a form considering the respective molarities so that the overall process becomes an integrated process with balanced molarities. Note that parentheses have been added in equations [1.1] and [3] in order to highlight that the syngas produced in [1.1] serves as a WO 2012/045373 PCT/EP2010/067182 11 reactant in equation [3]. C + 0 2 [2]

CH

4 + CO 2 + (2CO + 2H 2 ) [1.1] 2H 2 0 *4 2H 2 + 02 [4] (2CO + 2H 2 ) + 2 H 2 + 2CH 3 0H [3] [00049] In a preferred embodiment suitable storages for the needed and produced agents as well as for the heat energies from the processes [3] and [4] are provided at least for the demand of several hours, so that the above mentioned reactions and related processes can run timewise intermittent and with variable load to optimize the economic output. [00050] Especially the combustion process [2] can thus run during times when the electric energy produced from the combustion heat is high priced, and the electrolysis process [4] can be operated when the electric energy for it is at low cost available. Both processes [2] and [4] can thus by means of corresponding control devices (preferably realized by a combination of control hardware and software) considerably contribute to equalize the load fluctuations in an electric grid and can also take part in the frequency control of an electric grid. [00051] The chemical reforming and synthesis processes [1.1] and [3] shall be preferably operated at full load or at least of a load of more than 80%. [00052] Thus, the present invention enables completely new economically and ecologically meaningful possibilities for the "clean" generation of electric energy especially from coal in mid-load operation and for the production of methanol, which can be renewable, as well as for the equalizing of the load fluctuations and the frequency control of electric grids. [00053] The present invention is very well suited for the ,clean" combustion of hard coal and/or lignite. [00054] In a preferred embodiment an energy-integrated overall process matrix is realized using a combination of control hardware and software. The WO 2012/045373 PCT/EP2010/067182 12 overall energy consumption can be minimized by tuning the process conditions of the exothermic and endothermic reactions. The reactor design of a preferred embodiment results in a combination of - a combustion plant with an oxygen inlet connectable to an oxygen outlet of a water electrolysis plant and with a flue gas outlet connectable to a sequestration facility; - a reforming plant with a gaseous hydrocarbon supply, a carbon dioxide inlet, and a syngas outlet; - a water electrolysis plant with a water inlet, a hydrogen outlet, and an oxygen outlet; - a methanol reactor with catalyzer for carrying out a catalyzer-based synthesis process, the reactor comprising a methanol outlet and either separate syngas and hydrogen inlets, or a mixing/blending stage for combining the syngas and the hydrogen gas followed by a common syngas inlet. [00055] According to the invention the atom utilization of the above integrated reaction matrix is nearly 100 % and the commercial value of natural gas and carbon dioxide is elevated. This means that the mass and energy balances are optimized. The nearly 100 % atom utilization is to be calculated over a certain time span. In a real-time set up, where no substantial buffer capabilities are employed, a nearly 100 % atom utilization is given at any point in time. In an embodiment where buffer capabilities are employed, the nearly 100 % atom utilization is ensured over a certain time span only. In the context of the present invention "nearly 100 %" is used for a range between 90 % and 100 %, or preferably between 95 % and 100 %. [00056] The process and apparatus, as proposed and claimed herein, could also be used in a coal to synfuel plant which in post-processing steps transforms the methanol into diesel, gasoline, dimethyl ether or other light ends. [00057] The above-described process matrix is very well suited in situations where the flue gas of a combustion process is treated in order to capture the

CO

2 . The respective process matrix could be used in connection with a combustion-based power plant (e.g. a hard coal or lignite-fired power plant).

WO 2012/045373 PCT/EP2010/067182 13 [00058] An operation optimization is achieved when using the present invention since conventional power plants cannot be shut down quickly. For technical reasons (e.g. temperature tensions) they are difficult to be ramped down fast. Other plants, such as waste incineration power plants or plants which are primarily designed to produce process heat or heat for district heating systems, cannot at all be shut down. They have to produce electric energy as by product even if there is currently a "surplus" of electric energy available (low load times of the electric grid). The operators/owners of such plants sometimes even have to pay when they feed their electric energy into the electric grid. This in turn leads to situations where for instance wind farms have to be disconnected while fossil plants must produce electric energy. [00059] The present invention enables a flexible integration of such plants into existing electric grids if the respective plant comprises an inventive apparatus or if the plant is designed in accordance with the invention. During low-load times of the grid the electric energy can be used to drive the water electrolysis. It is also possible to use "surplus" electric energy from a wind farm, for instance, during a strong wind period. [00060] In a preferred embodiment of the invention the hydrogen and/or oxygen produced by the electrolysis is stored in dedicated buffer tanks. The size or capacity of these tanks is chosen so that the methanol synthesis plant can run in a constant or near constant mode. This is preferred since this part of the overall plant is expensive and difficult to operate in part load. The corresponding capital investment is only meaningful if the methanol synthesis runs in a constant or almost constant mode. [00061] In yet another preferred embodiment the CO 2 is fed into a buffer tank. Preferably, the CO 2 is stored in liquid form under pressure. Liquid CO 2 can easily be stored even over longer periods of time. It is the advantage of this embodiment that CO 2 can be captured and liquidified during low-load times of the grid. During such times it makes sense to invest more of the energy produced into the capturing and storage of CO 2 and/or to invest energy into the synthesis of hydrogen gas and/or to invest the energy in the synthesis of methanol.

WO 2012/045373 PCT/EP2010/067182 14 [00062] Further details and advantages of the present invention are described in the following on the basis of exemplary embodiments. [00063] Various aspects of the present invention are schematically illustrated in the figures of the drawing: Figure 1A: shows a functional diagram of a first process step according to the present invention; Figure 1B: shows a functional diagram of a second process step according to the present invention; Figure 1C: shows a functional diagram of a third process step according to the present invention; Figure 1D: shows a functional diagram of a fourth process step according to the present invention; Figure 2: shows a functional diagram of a system according to the present invention; [00064] Basic aspects of the invention are addressed and described in connection with Figures 1A -1D. [00065] According to the invention, a first process step 110 is the ,,clean" combustion of a carbon-containing material 109, such as coal (hard coal, lignite), natural gas, or biomaterials. The ,,clean" combustion 110 requires the supply of pure oxygen 108 or the supply of an oxygen-containing gas 108 having an oxygen concentration of at least 60%. The corresponding combustion 110 (oxidation) of pure carbon with pure oxygen is described in equation [2] and illustrated in Fig. 1A. The ,,clean" combustion process 110 has the advantages that on the one hand the combustion 110 as such is more efficient, if the adequate combustion chamber 10 (cf. Fig. 2) is used which is designed to withstand the high combustion temperature between 800 and about 1000 0 C or WO 2012/045373 PCT/EP2010/067182 15 to reduce the combustion temperature e.g. by means of flue gas recirculation. [00066] The plant 100 comprises in a preferred embodiment means for flue gas recirculation (not shown). The flue gas recirculation feeds some of the flue gas 113 and/or CO 2 101 back into the combustion chamber 10. The respective the flue gas 113 and/or CO 2 101 is relatively inert and has to have a lower temperature than the temperature at the flue gas outlet 113. The recirculated gas acts as a heat sink. It absorbs heat from the flame inside the combustion chamber 10 and it lowers the peak flame temperatures and also the temperatures at the flue gas outlet 113. This recirculation of gas leads to an effective reduction of the temperature inside the combustion chamber 10 or at the flue gas outlet 113. When an appropriate controller (e.g. the controller 200) is employed to control the recirculation (e.g. by an additional control point), the temperature inside the combustion chamber 10 can be "adjusted" by increasing or reducing the amount of flue gas 113 and/or CO 2 101 which is fed back into the combustion chamber 10. This flue gas recirculation scheme can be employed in all embodiments of the invention. [00067] All embodiments may comprise a combustion chamber 10 which is protected by means of a high-temperature anti-corrosion coating, overlay or layer. [00068] On the other hand, the flue gas 113 contains a higher C0 2 concentration and fewer or less critical contaminants and impurities (for instance nitrogen or NOx), which makes a subsequent C0 2 -sequestration process more efficient and robust. The C0 2 -sequestration process is carried out by a so-called C0 2 -sequestration facility 20 (cf. Fig. 2). Any of the known sequestration solutions can be used, if the quality of the C0 2 -gas is compatible with the reforming reaction 106 (cf. Fig. 1B). [00069] According to the invention, a second process step is the conversion of gaseous hydrocarbons (preferably methane 104) and carbon dioxide 101 into syngas 107 (a mixture of primarily carbon monoxide and hydrogen), as illustrated in Fig. 1B. A reforming process 106 is here used for the conversion of the gaseous hydrocarbons 104 by means of carbon dioxide 101 (cf. reaction WO 2012/045373 PCT/EP2010/067182 16 [1.1]). [00070] In order to optimize the reforming process 106 in respect to the energetic balance and also to the reaction conditions (e.g. to avoid the formation of soot) the primary reforming reaction 106 of methane [1.1] can be combined to a certain extent with the reactions: steam reforming CH 4 + H 2 0 (gaseous) = CO + 3H 2 + 206.2 kJ/mol [1.2] and/or direct oxidation CH 4 + 0.502 = CO + 2H 2 - 36 kJ/mol [1.3]. [00071] The reforming process 106 is endothermic. The required energy W2 can be provided by the "clean" combustion process 110. In this case the heat W1 of the process 110 could at least to some extent be used to drive the process 106 and/or the process 111. [00072] According to the invention, a further process step 105 is the water electrolysis where water 102 is split into hydrogen gas 103 and oxygen gas 108 using electric energy El, as summarized by the following equation [4] and illustrated in Fig. 1C:

H

2 0 = H 2 + 0.502 AH = +286.02 kJ/mol [4]. [00073] In a preferred embodiment of the invention, the electric energy El consumed by the water electrolysis 105 is at least to some extent provided from renewable sources. [00074] Most preferred is an embodiment where all of the electric energy El for the water electrolysis 105 is renewable. Some of the electric energy El might be provided by means of the ,clean" combustion process proceeding in the combustion chamber 10 which is part of a gas and/or steam power plant 70. [00075] According to the invention, yet a further process step is the synthesis WO 2012/045373 PCT/EP2010/067182 17 111 of methanol 112 (e.g. in accordance with reaction [3]), as illustrated in Fig. 1D. This synthesis 111 is carried out using the ideal or close-to-ideal stoichiometric ratio of reactants 107 and 103 in a very pure form. [00076] These steps 110, 106, 105, and 111, which so far were regarded as individual steps, according to the present invention form a nearly ideal process matrix for the efficient production of methanol 112 and energy W1. The above mentioned process steps 110, 106, 105, and 111 are intertwined and dependent on each other. [00077] It is a special advantage of this process matrix that the methanol 112 so produced is to some extent renewable and that at the same time it is C0 2 neutral since CO 2 emissions from the fossil combustion process 110 are recycled. [00078] It is a further advantage of the present invention that the oxygen gas 108 from the electrolysis 105 (cf. reaction [4]) is used in the process matrix in order to feed or drive the "clean" combustion process 110 (reaction [2]) and - if carried out - the direct oxidation process (reaction [1.3]). [00079] The inventive process matrix is regarded to be a synergistic process where all reactants are constituents of a stoichiometrically optimized setup, as given by the following reaction matrix: C + 0 2 + CO 2 [2]

CH

4 + CO 2 + (2CO + 2H 2 ) [1.1] 2H 2 0 .4 2H 2 + 02 [4] (2CO + 2H 2 ) + 2 H 2 + 2CH 3 0H [3] [00080] It goes without saying that in a practical implementation of the processes of the above matrix certain fluctuations or variations are tolerable. In an ideal or close to ideal embodiment of the invention the molarities of the following table are ensured. The table is to be read as follows: The first line of the table shows that, if in reaction [2] 1 mol of C is employed, one has to provide 1 mol 02 in order to produce 1 mol CO 2 . The last line of the table shows for WO 2012/045373 PCT/EP2010/067182 18 instance that 1 mol of H 2 is employed together with 1 mol syngas (CO + H 2 ) in order to produce 1 mol methanol. The respective molarities are considered to be factors. If for instance 10 mol of methanol are to be produced, one would need 10 mol H 2 and 10 mol syngas (CO + H 2 ). 10 mol syngas (CO + H 2 ) can be produced using 10/2 mol CO 2 and 10/2 mol CH 4 (i.e. 5 mol CO 2 and 5 mol CH 4 ). Reaction 02 CO 2

CH

4 (CO + H 2 0 H 2

CH

3 0H

H

2 ) C [2] 1 1 02 [2] 1

CO

2 [1.1] 1 2

CH

4 [1.1] 1 2

H

2 0 [4] 1/2 1 (CO + [3] 1 1

H

2 )

H

2 [3] 1 1 [00081] The inventive process matrix is regarded to be a cogenerating process matrix since it in the first place produces or provides energy W1 (electricity energy and/or heat) from the ,,clean" combustion 110 of the carbon containing material 109 (reaction [2]), but also loss heat E2 from the electrolysis process 105 (reaction [4]), reaction heat W3 from the synthesis process 111 (reaction [3]) and - if carried out - reaction heat from the direct oxidation process (reaction [1.3]). [00082] The inventive process matrix also provides methanol 112 which at least to some degree is considered renewable. The gaseous hydrocarbons 104 (preferably methane) are employed in order to provide the energy which is required for the reduction of CO 2 101. CH 4 is an example for a reducing agent. Other (preferably gaseous) hydrocarbons 104 could be used instead or in addition.

WO 2012/045373 PCT/EP2010/067182 19 [00083] The CO 2 101 and the gaseous hydrocarbons 104 (preferably methane) together serve as carbon sources for the production of methanol 112. All of the carbon of the CO 2 101 and of the gaseous hydrocarbons 104 (preferably methane) is transformed into CO. The CO is then used to synthesize the methanol 112. [00084] It is an advantage of the invention that rather than using CO 2 for synthesizing methanol, the CO 2 101 is transformed (reduced) in an intermediate reforming step 106 into CO. Impurities of the CO 2 -gas 101 which have not been removed during the sequestration process are thus not introduced into the catalyzer required for the methanol synthesis 111. The reforming process 106 was found to be more tolerant to impurities than the methanol synthesis 111. [00085] The inventive method for the cogeneration of electric energy and methanol 112 in a plant 100, comprises at least the following steps: - feeding hydrocarbons 109 into a combustion chamber 10, - feeding oxygen gas 108 into the combustion chamber 10, the oxygen concentration of the oxygen gas 108 being greater 60 %, - maintaining an oxygen-based combustion process 110 for the combustion of the hydrocarbons 109 in the combustion chamber 10, - feeding flue gas 113 produced by the combustion process 110 into a sequestration facility 20 in order to separate carbon dioxide 101 from the flue gas 113, - feeding the carbon dioxide 101 into a reforming plant 30, - feeding gaseous hydrocarbons 104 into the reforming plant 30, - carrying out a reforming process 106 which processes the carbon dioxide 101 together with the gaseous hydrocarbons 104 in order to provide a carbon monoxide and hydrogen gas containing syngas 107, - providing hydrogen gas 103 and oxygen gas 108 obtained from a water electrolysis process 105, - feeding a feed gas 114 (see Fig. 2) comprising the syngas 107 and the hydrogen gas 103 obtained from the water electrolysis 105 into a methanol reactor 50 in order to produce methanol 112. [00086] These process steps depend on each other since WO 2012/045373 PCT/EP2010/067182 20 - the oxygen gas 108 fed into the combustion chamber 10 is obtained from the water electrolysis 105, - the carbon dioxide 101 used in the reforming process 106 is obtained from the flue gas 113 of the combustion process 110, - the hydrogen gas 103 obtained from the water electrolysis 105 together with the syngas 107 obtained from the reforming process 106 is used for producing the methanol 112. [00087] Please note that the fossil power plant 60 of Fig. 2 comprises a reactor 10 and a sequestration facility 20 (e.g. a washer), for instance. The fossil power plant 60 could also comprise other units and appliances, such as a gas and/or steam turbine power plant 70. Such a gas and/or steam turbine power plant 70 is schematically illustrated in Fig. 2 by means of a rectangular box which feeds electric energy E3 to an electric grid 71. The gas and/or steam turbine power plant 70 is for instance connected to the combustion chamber 10. The respective connection is not shown in Fig. 2. All embodiments of the invention may comprise a gas and/or steam turbine power plant 70 and/or a connection to an electric grid 71. [00088] According to a preferred embodiment of the invention the feed gas 114 which is fed into the methanol reactor 50 comprises a ratio of reactants 103, 107 of approximately 1 mol of syngas 107 plus 1 mol of hydrogen gas 103 in order to produce 1 mol of methanol 112. The ideal or near ideal ratio of the feed gas 114 is ensured by a stoichiometrically optimized combination of the syngas 107 and the hydrogen gas 103. A ratio of ±10 % is herein considered a "near ideal ratio". [00089] The synthesis 111 is typically carried out at an increased temperature and pressure in order to be efficient. Synergistic effects can be obtained if a pressurized water electrolysis 105 is employed. The pressurized water electrolysis 105 provides a pressurized hydrogen gas 103 at an output 41. The hydrogen gas 103 typically has a pressure of more than 10 bar at the output 41. This pressurized hydrogen gas 103 can be used to feed the methanol reactor 50. In this case no energy is consumed to drive a compressor, or a compressor consumes less energy since it receives at the input side pressurized gas 103. The WO 2012/045373 PCT/EP2010/067182 21 unit 53 in Fig. 2 might serve as a mixing facility and/or compressor. The unit 53 provides the right mixture or blend and pressure of the gases 103 and 107. [00090] Synergistic effects can also be obtained if (excess heat), from one process (e.g. some of the heat W1 of the combustion 110) is used to establish the adequate conditions for another process (e.g. the process 105 and/or 106 and/or 111). According to a preferred embodiment of the invention the increased temperature of the flue gas 113 at the output side of the reactor 60 is used to pre-heat or heat the reactor 50 since the synthesis 111 is typically carried out at an increased temperature. [00091] According to a preferred embodiment of the invention the combustion process 110 provides energy W1 which is used to generate electric energy and/or heat. At least some of this heat can be used to energetically support one of the other process steps (e.g. the processes 106 and/or 105), as addressed in the previous paragraph. [00092] According to another preferred embodiment of the invention the electric energy El which is required to run the water electrolysis 105 is taken from electric energy generated by means of the combustion process 110 and/or from an electric grid (e.g. the grid 71) and/or from a renewable source (e.g. wind power or solar power plant). [00093] The process 111 requires relatively pure reactants since there is a risk of weakening the catalyzer by pollutants. The feed gas 114 thus should contain e.g. less than 1 ppm sulfur. A cleaning stage could be placed before the reactor 50 or the unit 53 in order to ensure the required quality of the feed gas 114. Such a cleaning stage should also remove or reduce heavy metal components contained in the feed gas 114. [00094] The dashed lines in Fig. 2 indicate the flows of media. The respective flows are preferably made switchable or controllable by means of control points C1, C2 and so forth (a control point is a valve, shutter, pump, compressors or other kind of entity which enables a controller 200 to reduce or increase a flow or throughput).

WO 2012/045373 PCT/EP2010/067182 22 [00095] According to another preferred embodiment of the invention the power plant 60 is connectable to an electric grid 71 via a gas and/or steam turbine power plant 70 in order to feed electric energy into this grid 71. The power plant 60 is part of a larger build-up or aggregation of systems, appliances and facilities. This larger build-up or aggregation is herein referred to as plant 100. [00096] The plant 100 preferably comprises a software-based process controller 200, as schematically illustrated in Fig. 2. The software-based process controller 200 is designed and implemented so that it is able to control the flow/supply of at least one of the reactants. For this reason the plant 100 comprises at least one control point (e.g. Cl). A control point is a valve, shutter, pump, compressor or other kind of entity which enables the controller 200 to reduce or increase a flow or throughput. The control point C1 for instance enables the controller 200 to control the reforming process 106 or to reduce the syngas flow 107. [00097] The following table gives further details regarding some of the other control points of an inventive plant 100. The content of this table is to be understood as an example only. control point Controls the flow of Remarks / application example C2 the flue gas 113 Could be used to bypass the sequestration facility 20 C3 the CO 2 Could be used to ensure that the reactor 30 receives the right mixture of CO 2 and

CH

4 C4 the CH 4 input Could be used to ensure that the reactor 30 receives the right mixture of CO 2 and

CH

4 C5 the hydrocarbon C5 could control a device for feeding input hydrocarbons 109 into the reactor 10 C6 the 02 input Could be used to ensure that the reactor 10 receives the right mixture of C and 02 WO 2012/045373 PCT/EP2010/067182 23 C7 the H 2 Could be used to ensure that the unit 53 receives the right mixture of H 2 and syngas CO + H 2 C8 electric energy El C8 could serve as switch to change over from a grid-based electric supply to a renewable energy-based electric supply [00098] The controller 200 is connectable to the control points C1, C2 etc. The respective connections are not shown in Fig. 2. The controller 200 preferably comprises an associated parameter storage 201 for the retrieval of stored information and parameters and an input for receiving input signals I1, 12 from other systems. The input signals I1, 12 could come from other systems of the plant 100 or they could come from a grid control facility indicating the load status of the grid 71 and/or the grid frequency. [00099] According to another preferred embodiment of the invention the controller 200 is employed in order to contribute to an equalization of load fluctuations of the electric grid 71 and/or to the frequency control of the electric grid 71. For this purpose the software-based process controller 200 is designed and implemented so that it is able to control the output of the combustion process 110 and/or of the water electrolysis 105 so as to contribute to the load equalization and/or the frequency control of the electric grid 71. Furthermore, the possible immediate shut-off of the water electrolysis 105 offers the respective load reserve for the grid 71. [000100] According to another preferred embodiment of the invention the controller 200 is employed in order to control the flow of gases and reactants (e.g. via the control points mentioned) so that the methanol reactor 50 and/or the reforming plant 30 are operated at a load of more than 80 % and preferably at a load of close to 100 %. [000101] According to another preferred embodiment of the invention the controller 200 is employed so as to receive a demand input I1, 12. The controller 200 takes decisions based on the demand input. The process steps are controlled WO 2012/045373 PCT/EP2010/067182 24 and carried out by the process controller 200 and the plant 100 so that the combustion process 110 provides via the power plant 60 (which is either part of the plant 100 or which is connected to the plant 100) a first amount of electric energy (e.g. the electric energy E3) into a grid 71 and a second amount of electric energy (e.g. the electric energy El) to the water electrolysis process 105. [000102] According to another preferred embodiment of the invention the heat (e.g. some of the heat W1) of the combustion process 110 supports the reforming process 106, while the reaction heat W3 of the synthesis process 111 and/or the loss heat of the reforming process 106 and/or the loss heat E2 of the electrolysis process 105 can support the power plant process 110 for generation of electric energy. [000103] According to another preferred embodiment of the invention heat from several sources (e.g. from one or more of the sources 10, 40, 50) is transformed into electric energy by means of a gas and/or steam turbine power plant 70. Preferably, heat from the combustion chamber 10 and/or the electrolysis plant 40 and/or the synthesis plant 50, and/or - if existent - a direct oxidation plant is transformed into electric energy E3 by means of the gas and/or steam turbine power plant 70. The respective electric energy E3 might be fed into the electric grid 71. [000104] According to another preferred embodiment the plant 100 (cf. Fig. 2) is specifically designed for the cogeneration of electric energy and methanol 112. The apparatus 100 comprises a combustion chamber 10 which is designed for an oxygen-enriched combustion process 110. The combustion chamber 10 has a flue gas outlet 11. The apparatus 100 further comprises a hydrocarbon infeed 12 connectable to the combustion chamber 10, and an oxygen enriched gas infeed 13 connectable to the combustion chamber 10. A sequestration facility 20 is provided which is designed for the separation of carbon dioxide 101 from flue gas 113 received via the flue gas outlet 11. The sequestration facility 20 has a carbon dioxide outlet 21. A reforming plant 30 is provided which includes a syngas outlet 31. The reforming plant 30 is connectable to the carbon dioxide outlet 21 of the sequestration facility 20 and it WO 2012/045373 PCT/EP2010/067182 25 is designed for carrying out a reforming process which produces syngas 107 comprising carbon monoxide and hydrogen gas 103. The reforming plant 30 has a gaseous hydrocarbon inlet 32 so that a gaseous hydrocarbon can be fed into the reforming plant 30. A water electrolysis facility 40 is provided which can be supplied by electric energy El. It receives water 102 through a tap 43 and it is designed in order to produce hydrogen gas 103 and oxygen gas 108. The water electrolysis facility 40 comprises a hydrogen gas outlet 41 and an oxygen gas outlet 42, as illustrated in Fig. 2. A methanol reactor 50 for synthesizing methanol 112 is provided. The methanol reactor 50 comprises a methanol outlet 51, a feed gas inlet 52 for feeding the hydrogen gas 103 obtained from the water electrolysis facility 40 and the syngas 107 into the methanol reactor 50. [000105] Details of a suitable methanol reactor 50 are disclosed and claimed in the international patent application PCT/EP2010/064948, which is currently assigned to the applicant of the present application. [000106] There is also a software-based process controller 200 which is the control instance of the processes carried out in the inventive plant 100. The controller 200 may control the flows of the reactants by adjusting valves, pumps, compressors and shutters (here called control points). Fig. 2 shows arrows placed around the controller 200 to indicate that there are control links which enable the controller 200 to interact with the control points C1, C2 and so forth. [000107] The plant 100 with a controller 200 enables the operator to take decisions based on (local) needs or requirements. The decision making process may involve information received from other (remote) systems or instances (such as an energy stock exchange providing pricing information). The invention gives the operator the discretion to take decisions and to run the plant 100 so that the (local) needs or requirements are satisfied.

WO 2012/045373 PCT/EP2010/067182 26 Reference number listing: Combustion chamber 10 flue gas outlet 11 coal or hydrocarbon infeed 12 oxygen gas infeed 13 sequestration facility 20 carbon dioxide outlet 21 reforming plant 30 syngas outlet 31 gaseous hydrocarbon inlet 32 water electrolysis facility 40 Output 41 Outlet 42 Tap 43 methanol reactor 50 methanol outlet 51 feed gas inlet 52 unit 53 Power plant 60 gas and/or steam turbine power plant 70 electric grid 71 plant 100 Carbon dioxide 101 water 102 Hydrogen gas 103 gaseous hydrocarbon 104 Carrying out an electrolysis 105 Reforming process 106 Syngas 107 Oxygen gas 108 Carbon containing material 109 ,,clean" combustion 110 Methanol synthesis 111 Methanol 112 Flue gas 113 Feed gas 114 software-based process controller 200 parameter storage 201 Control point C1, C2, C3, C4, C5, C6, C7, C8 WO 2012/045373 PCT/EP2010/067182 27 DC current / electric energy El Loss heat E2 Electric energy E3 input signals I1, 12 Heat and/or energy W1; W2, W3

Claims

1. Method for the cogeneration of electric energy and methanol (112) in a plant (100), comprising the process steps: - feeding coal (109) or hydrocarbons into a combustion chamber (10), - feeding oxygen gas (108) into the combustion chamber (10), the oxygen concentration of the oxygen gas (108)being greater 60 %, - maintaining an oxygen-based combustion process (110) for the combustion of coal (109) or hydrocarbons in said combustion chamber (10), - feeding flue gas (113) produced by said combustion process (110) into a sequestration facility (20) in order to separate carbon dioxide (101) from said flue gas (113), - feeding said carbon dioxide (101) into a reforming plant (30), - feeding gaseous hydrocarbon (104) into the reforming plant (30), - carrying out a reforming process (106) which processes the carbon dioxide (101) together with the gaseous hydrocarbon (104) in order to provide a carbon monoxide and hydrogen gas containing syngas (107), - providing hydrogen gas (103) and oxygen gas (108) obtained from a water electrolysis process (105), - feeding a feed gas (114) comprising said syngas (107) and said hydrogen gas (103) obtained from the water electrolysis (105) into a methanol reactor (50) in order to produce methanol (112).

2. The method of claim 1, wherein heat from at least one process step (110, 105, 106) is transformed into electric energy (E3) by means of a gas and/or steam turbine power plant (70).

3. The method of claim 1, wherein heat from - the combustion chamber (10), and/or - an electrolysis plant (40) for carrying out the water electrolysis (105), and/or - a synthesis plant serving as methanol reactor (50), and/or - a direct oxidation plant WO 2012/045373 PCT/EP2010/067182 29 is transformed into electric energy (E3) by means of a gas and/or a steam turbine power plant (70).

4. The method of claim 1, 2, or 3, wherein the process steps of claim 1 depend on each other since - the oxygen gas (108) fed into the combustion chamber (10) is obtained from the water electrolysis (105), - the carbon dioxide (101) used in the reforming process (106) is obtained from said flue gas (113) of the combustion process (110), - the hydrogen gas (103) obtained from the water electrolysis (105) together with the syngas (107) obtained from the reforming process (106) is used for producing the methanol (112).

5. The method of claim 1, 2, 3 or 4, wherein the feed gas (114) which is fed into the methanol reactor (50) comprises a ratio of reactants of approximately 1 mol of carbon dioxide plus 2 mol of hydrogen gas in order to produce 1 mol of methanol (112).

6. The method of claim 5, wherein said ratio of the feed gas (114) is ensured by a stoichiometrically optimized combination of the syngas (107) and the hydrogen gas (103).

7. The method of one of the preceding claims, wherein said water electrolysis (105) is a pressure-based water electrolysis providing pressurized hydrogen gas (103) at a pressure of more than 10 bar, and wherein said pressurized hydrogen gas is fed into said methanol reactor (50).

8. The method of one of the preceding claims, wherein said combustion process (110) provides energy in form of heat (W1) which is used to generate electric energy and at least some of this heat (W1) being used to energetically support one of the other process steps (20, 105, 106, 111) of claim 1.

9. The method of claim 8, wherein said heat (W1) is used to energetically support one or more of the following process steps: WO 2012/045373 PCT/EP2010/067182 30 - a C0 2 -sequestration process carried out in said sequestration facility (20), and/or - said water electrolysis (105), and/or - said reforming process (106), and/or - a methanol synthesis process (111) carried out by said methanol reactor (50).

10. The method of one of the preceding claims, wherein electric energy (El) which is required to run the water electrolysis (105) is taken from electric energy generated by means of said combustion process (110) and/or from a grid and/or from a renewable source.

11. The method of one of the preceding claims, wherein the feed gas (114) comprises less than 1 ppm sulfur.

12. The method of one of the claims 2 or 3, wherein said gas and/or steam turbine power plant (70) is connectable to an electric grid (71) in order to feed electric energy (E3) into said grid (71), and wherein a software-based process controller (200) is employed in order to contribute - to an equalization of load fluctuations of said electric grid (71), and/or - to a frequency control of said electric grid (71).

13. The method of claim 12, wherein the software-based process controller (200) controls the combustion process (110) and/or the water electrolysis (105) so as to contribute to the equalization and/or frequency control of said electric grid.

14. The method of one of the preceding claims 1 through 11, wherein a software based process control process is carried out in order to control the flow of gases and reactants so that the methanol reactor (50) and/or the reforming plant (30) are operated at a load of more than 80 % and preferably at a load of close to 100 %.

15. The method of one of the preceding claims, comprising one or more of the following steps: WO 2012/045373 PCT/EP2010/067182 31 - storing the oxygen gas (108) in an oxygen gas tank, - storing the hydrogen gas (103) in a hydrogen gas tank, - storing carbon dioxide (101) in a carbon dioxide gas tank, said carbon dioxide (101) being preferably liquidified and stored in liquid form under pressure.

16. The method of one of the preceding claims 1 through 11, wherein a software based process controller (200) receives a demand input (I1, 12) and wherein, based on said demand input (I1, 12), at least some of the process steps of claim 1 are controlled and carried out by said process controller (200) so that by means of the combustion process (110) a first amount of electric energy is generated for a grid and a second amount of electric energy for said water electrolysis process (105).

17. The method of one of the preceding claims, wherein heats from the combustion process (110) and/or from a methanol synthesis process (111) and/or - if existent - from a direct oxidation process are provided to heat the reforming process (106) and/or gases for the synthesis process (111) and/or a methanol destillation process which is downstream of the methanol synthesis process (111) and/or a C0 2 -sequestration process (20).

18. The method of one of the preceding claims, wherein a reforming reaction (106) of methane (104) is combined to a certain extent with a steam reforming reaction.

19. The method of one of the preceding claims, wherein a reforming reaction (106) of methane (104) is combined to a certain extent with a direct oxidation reaction, and wherein preferably oxygen for the direct oxidation reaction is provided by said water electrolysis (105).

20. Plant (100) for the cogeneration of electric energy and methanol (112) comprising: - a combustion chamber (10) designed for an oxygen-based combustion process, said combustion chamber (10) comprising a flue gas outlet (11), WO 2012/045373 PCT/EP2010/067182 32 - a coal or hydrocarbon infeed (12) connectable to the combustion chamber (10), - an oxygen gas infeed (13) connectable to the combustion chamber (10), - a sequestration facility (20) designed for the separation of carbon dioxide from flue gas (113) received via said flue gas outlet (11), said sequestration facility (20) comprising a carbon dioxide outlet (21), - a reforming plant (30) comprising a syngas outlet (31), said reforming plant (30) being connectable to said carbon dioxide outlet (21) and being designed for carrying out a reforming process (106) which produces syngas (107) comprising carbon monoxide and hydrogen gas, - a gaseous hydrocarbon inlet (32) connectable to the reforming plant (30), - a water electrolysis facility (40) suppliable by electric energy (El) and water (102) and designed in order to produce hydrogen gas (103) and oxygen gas (108), the water electrolysis facility (40) comprising a hydrogen gas outlet (41) and an oxygen gas outlet (42), - a methanol reactor (50) for synthesizing methanol (112), said methanol reactor (50) comprising a methanol outlet (51), - a feed gas inlet (52) for feeding the syngas (107) and the hydrogen gas (103) obtained from the water electrolysis facility (40) into the methanol reactor (50).

21. The plant (100) of claim 20, characterized in that it further comprises devices to transform heat from several sources (10, 40, 50) into electric energy by means of a gas and/or steam turbine power plant (70).

22. The plant (100) of claim 20, characterized in that it further comprises a gas and/or steam turbine power plant (70) for transforming heat from one or more of the following sources into electric energy (E3): - heat provided by the combustion chamber (10), and/or - heat provided by an electrolysis plant (40) for carrying out the water electrolysis (105), and/or - heat provided by a synthesis plant serving as methanol reactor (50), and/or - heat provided by a direct oxidation plant. WO 2012/045373 PCT/EP2010/067182 33

23. The plant (100) of claim 20, 21, 22, characterized in that it further comprises a software-based controller (200), said controller being able to control one or more flows of reactants of process steps carried out in the plant (100).

24. The plant (100) of claim 23, characterized in that it comprises at least one control point (Cl - C8) and at least one corresponding control link for enabling the controller (200) to interact with said at least one control point (C1 - C8).

25. The plant (100) of claim 23 or 24, characterized in that the controller (200) is programmed in order to operate the plant (100) at least in the following two alternative modes: - 1st mode, when the combustion process (110) is running during high-load times of the electric grid, - 2nd mode, when an electrolysis process (105) is being carried out by the water electrolysis facility (40) at low-load times of the electric grid.

26. The plants (100) according to one of the preceding claims 20 - 25, further comprising at least one buffer tank.