WO2015180752A1

WO2015180752A1 - Hydrocarbon-production-apparatus and method for producing hydrocarbons with renewable electric energy

Info

Publication number: WO2015180752A1
Application number: PCT/EP2014/060831
Authority: WO
Inventors: Carl Berninghausen; Christian Von Olshausen; Dietmar Rüger
Original assignee: Sunfire Gmbh
Priority date: 2014-05-26
Filing date: 2014-05-26
Publication date: 2015-12-03
Also published as: AU2014395432B2; CN106460208A; AU2014395432A1; CN106460208B

Abstract

The present invention relates to a hydrocarbon-production-apparatus for the production of gaseous and / or liquid hydrocarbons from solid, liquid or gaseous carbonaceous carrier comprising a gasifier for the production of a carbon monoxide sustainable gasification gas, a shift-process to produce hydrogen and carbon dioxide from carbon monoxide and water vapour, and a synthesis process for the production of gaseous and / or liquid hydrocarbons from carbon monoxide and hydrogen. Furthermore the invention relates to a hydrocarbon-production-method with a hydrocarbon-production-apparatus according to the invention.

Description

Hydrocarbon-production-apparatus and method for producing hydrocarbons with renewable electric energy

D E S C R I P T I O N

The present invention relates to a hydrocarbon-production-apparatus for the production of gaseous and / or liquid hydrocarbons from solid, liquid or gaseous carbonaceous carrier comprising a gasifier for the production of a gasification gas containing carbon monoxide, a shift-process to produce hydrogen and carbon dioxide from carbon monoxide and water vapour, and a synthesis process for the production of gaseous and / or liquid hydrocarbons from carbon monoxide and hydrogen. Furthermore the invention relates to a hydrocarbon-production-method with a hydrocarbon-production-apparatus according to the invention.

The field of the invention is the global, regional and local electric power generation and distribution, the global, regional and local supply for the chemical industry and the energy sector with liquid and gaseous hydrocarbons and energy as well as the transport sector with renewable fuels.

In the description of this invention the renewable electric energy is to be understood as excess renewable electric energy, produced by solar installations, wind turbines or hydroelectric power stations and the like which could not be used for actual electricity needs or is produced in regions, where the electricity could not be transported to the next possible customers. It is important to understand that the use of fossil energy is precisely negative for this invention, so it will not be used as the for the invention necessary electric energy.

The production of liquid and gaseous hydrocarbons from carbonaceous fuels, waste and residues in accordance with the prior art, uses the gasification of the feedstock with an oxygen containing gasifying substance or agent to a synthesis gas consisting mainly of carbon monoxide and hydrogen. The synthesis gas is then converted in liquid or gaseous hydrocarbons with conventional synthesis processes. The production of hydrocarbons using an entrained flow gasifier, a shift-process and methane synthesis is an established and proven technology. Depending on the quality of the starting materials, it may be necessary to prepare these to the specific requirements of the respective entry and gasification process. Preparation methods are drying, crushing / grinding, thermal decomposition of the starting material in carbonaceous gases and / or liquids and solids by pyrolysis, torrefaction, hydrothermal carbonization and the like.

In the hydrocarbon synthesis, synthesis gas consisting mainly of carbon monoxide and hydrogen is converted to hydrocarbons, with the release of energy. Synthesis processes for liquid hydrocarbons are also well known, for example Methanol synthesis (Lurgi - low-pressure process), Fischer-Tropsch synthesis, dimethyl ether synthesis, etc.

For the synthesis of gaseous hydrocarbons according to the prior art, the production of methane from carbon monoxide and hydrogen is mainly known and used.

Because of the low-priced natural gas the production of methane from carbon monoxide and hydrogen has not been used industrially before.

Because of the composition of the feedstock the synthesis gas from the gasification of carbonaceous feedstock typically contains too much carbon monoxide in relation to hydrogen. To set the required molar ratio of carbon monoxide to hydrogen in the synthesis gas for the particular synthesis method, a part of the carbon monoxide is usually converted in a shift-process with water vapour to form hydrogen and carbon dioxide according to the homogeneous water gas shift reaction. The resulting carbon dioxide is removed from the synthesis gas by suitable methods, such as Rectisol or Selexol scrubbing, mono ethanol amine scrubbing, or membrane separation processes, and discharged to the atmosphere. Variations in feedstock composition or litigation that lead to fluctuating gas qualities are balanced by controlling the shift process, so there is a constant gas quality available for synthesis.

There is a growing demand for energy and raw materials such as fossil fuels, oil, gas and in future also coal, but because of the limited resources this is an upcoming problem to serve all demands. Then there is a growing demand to reduce the emissions of carbon dioxide to keep the environment green and clean. It is the task to close the carbon cycle. Because of the expansion of facilities for production of electrical energy from solar energy and wind power and the daily and seasonal and weather-related variations, spatial and temporal over-capacity in the electric power distribution network there is the demand to store and transport the renewable electrical energy especially the excess renewable electric energy and not to shutdown energy production facilities.

Often systems for the production of electric energy arise far away from the customers and often at locations that are far away from sites of energy demand, so there must be a way to transport the energy over long distances, which is also associated with large costs for the transport and large amount of losses. One option to compensate local excess capacities in the electricity grid is the expansion of the distribution grid or network with sufficient transmission capacity. The expansion of the electricity grid is time-consuming and expensive and obviously could not solve the problem alone.

Another way to compensate local excess capacity in the electricity grid is to store electrical energy in large quantities, as in electrical, chemical, electrochemical or mechanical storages.

Therefore the development of storage technologies with high storage capacities and also high efficiency of storage is demanded. Also the re-generation of electricity of the stored energy is in the focus. The storage of renewable electric energy in the form of methane by the use of the conversion of carbon monoxide and / or carbon dioxide with hydrogen is an important factor, so the gas-transportation grid, the natural gas network is basically an unlimited storage for the produced methane and is available nearly at any location. The so stored energy easily could be reused.

Problems of the prior art The document WO 2005/056 737 describes a method and installation for producing liquid energy carriers from a solid carbon carrier by means of gasifying a solid carbon carrier. The required molar ratio for the synthesis of hydrogen and carbon monoxide is not adjusted by a carbon monoxide shift process, but only by supplying hydrogen from the electrolysis of water. Oxygen from electrolysis is used as a gasification agent.

But the absence of a shift process while producing hydrocarbons requires a constant power supply for the process to operate the electrolysis and produce hydrogen and oxygen in the exact demands. Because the electrolysis is operated with renewable electric energy this method can only respond to fluctuations in the renewable electric energy by controlling the fuel supply and thus with a reduction of the performance of the gasifier.

On the other hand the gasification process and subsequent synthesis of the prior art, depending on the feedstock quality, and the production of liquid and gaseous hydrocarbons with a shift-process lead to a lack of carbon while the shift-process generates hydrogen and carbon-dioxide (see R5). The so formed carbon dioxide is removed from the synthesis gas and discharged to the atmosphere. So this portion of carbon is no longer available for the production of liquid and gaseous

hydrocarbons and also pollutes the atmosphere.

To improve the carbon-utilization hydrogen produced by electrolysis as in the document WO 2005/056 737, the option to control the process with a shift-process is totally waived. So there has to be used also electrical energy generated with fossil fuels, which leads to an overall increase in power generation from fossil sources. So the saved carbon dioxide emission from the shift process by adding hydrogen from electrolysis is totally canceled by the additional emission of carbon dioxide during the production of fossil electricity to power the electrolysis:

While producing 1 mol H2 by the use of the water electrolysis, 1 mol C02 emission is saved in the shift process. For the production of 1 mol of H2 by using the water electrolysis, with an efficiency of 70%, the electric energy of 344.5 kJ is needed, which liberates more than 2 mol of carbon dioxide (combustion of carbon : 2.4 mol; combustion of coal 2.1 mol) assuming an efficiency of electricity generation by 35 %.

Due to the daily and seasonal and weather-related fluctuations in the production of electric energy from renewable sources the supply of energy generated from renewable electric energy is related to increasing regional and temporal

overcapacity in the electricity grid, which means that fossil basic-load-generators are often operated under their economic limit and so be put out of operation.

Object of the invention The object of this invention is to develop a hydrocarbon-production-apparatus and a method or process for the production of gaseous and liquid hydrocarbons from solid, liquid and gaseous carbonaceous fuel, waste and residues, which increases the carbon utilization efficiency and reduces the emission of environmentally harmful carbon dioxide. Furthermore, the method should be suitable to use a high proportion of renewable electric energy to reduce and store it in the form of gaseous and liquid hydrocarbons. So the excess capacities of the renewable electric energy in the electricity grid will be compensated.

Solution

A hydrocarbon-production-apparatus for the production of gaseous and / or liquid hydrocarbons from solid, liquid or gaseous carbonaceous carrier comprising an entrained flow gasifier for the production of a carbon monoxide sustainable gasification gas, a shift-process to produce hydrogen and carbon dioxide from carbon monoxide and water vapour, and a synthesis process for the production of gaseous and / or liquid hydrocarbons from carbon monoxide and hydrogen is characterized by a bypass stream for the gasification gas to bypass the shift- process and a water electrolysis operable only with renewable electric energy for hydrogen production.

The incorporation of hydrogen from renewable electric energy in this process allows the compensation of excess capacity in the electric power distribution network, due to spatial and temporal variations in the production of renewable electrical energy and converts this electrical energy into conventional hydrocarbon energy sources with existing infrastructure for distribution and use.

The conversion of solid, liquid and gaseous carbon-containing fuels, waste and residual materials, such as coal, carbon, biomass, tars, oils, etc. in liquid and gaseous hydrocarbons by the use of hydrogen generated with renewable electric energy is a possibility to supply the chemical industry with raw materials, e.g.

methan and the like, and to store environmentally friendly energy in liquid or gaseous form. In times when there is no excess renewable electrical energy in the electricity grid available the production of hydrocarbons will continue by using the shift-process to produce the necessary hydrogen for the synthesis.

The apparatus comprises at least one electric heater operable only with renewable electric energy to heat carbon, oxygen, water vapour and/or carbon dioxide. Especially the apparatus comprises four electric heaters operable only with renewable electric energy to heat carbon, oxygen, water vapour and carbon dioxide.

The water electrolysis is a steam electrolyser. The advantage of the steam electrolyser is that the energy for the evaporation of water that must be applied also by use of electric energy in the water electrolysis will be covered from heat energy, which advantageously is made of unused waste heat e.g. originating of a

subsequent synthesis process. The steam electrolyser thus has an advantage in the efficiency over the traditional water electrolysis.

The gasifier is an entrained flow gasifier, which is working with a high efficiency.

It is further inventive when the hydrogen produced in the electrolysis is buffered with compression with the pressure required for the process prior to use in the process.

The buffering reduces a possibly occurring pressure variation after compression and allows a better balance between short-term fluctuations in the quality of the synthesis gas. Pressure and quality variations in the synthesis gas may have a negative impact on the lifetime of the catalysts used in the synthesis and may lead to fluctuations in the quality in the synthesis produced product.

The apparatus comprises a gas treatment and gas purification means for removal of unwanted gas components, carbon dioxide and water vapour of the gasification gas. The synthesis process includes means for removing the reaction-water for re-using the removed water in the electrolysis or as process water.

A hydrocarbon-production-method with a hydrocarbon-production-apparatus according to the invention with the steps: comprising at least two processing- variants, wherein in the first variant the shift-process produces hydrogen and carbon dioxide from carbon monoxide and water vapour and in the second variant the shift- process is turned off by bypassing the water-vapour-saturated gasification gas around the shift-process through the use of the bypass stream and the water electrolysis produces hydrogen with renewable electric energy, wherein the second variant is executed only if renewable electric energy is available.

The oxygen and the carbonaceous material are pre-heated to increase the hydrogen absorption capability.

Carbon dioxide is used as an endothermic gasification agent to increase the hydrogen absorption capability of the process and thus to further integrate more renewable electric energy instead of steam for controlling the gasification temperature and to achieve complete carbon conversion in the gasification of carbon dioxide.

Furthermore the carbon dioxide, which is produced in the shift process and being separated in the gas purification means in times when no or only less excess renewable electric energy is available, can be buffered in intermediate storages. The so buffered carbon dioxide can be reused as the endothermic gasification agent in times when sufficient excess renewable electric energy is available for the water or steam electrolyser. So the water or steam electrolyser produces the hydrogen using only excess renewable electric energy and the buffered carbon dioxide is reused as the endothermic gasification agent.

Extra renewable electric energy is additionally used for heating carbon, oxygen, water vapour and/or carbon dioxide, so more renewable electric energy is buffered in a chemical form with high efficiency. Oxygen, being generated in the electrolysis with excess renewable electric energy, is used as a gasification agent for the gasification, wherein preferable said oxygen being stored in an intermediate buffer. The performance of an air separation plant could be reduced because of the use of the stored oxygen. For the adjustment of a stable hydrogen-carbon monoxide molar ratio before the synthesis-process the performance of the electrical preheating of the water vapour, of the carbon dioxide, of the oxygen and carbon-containing solid and / or liquid feedstock, the ratio of the endothermic gasification agent water vapour to carbon dioxide, the amount of gasification gas to the shift process and / or the gasification capacity of the plant can be controlled and regulated individually or in combination.

The economic advantage of the invention is the use of excess renewable electric energy in the power grid, which is due to daily, seasonal and weather-related fluctuations in the generation of renewable electric energy.

The possibility of buffering the excess renewable electric energy in the natural gas grid with high efficiency is very important. High costs for the upgrading of the electricity grid can be avoided.

Due to the better utilization of carbon in the process the specific needs of carbonaceous feedstock is as low as possible and very efficient. This reduces the consumption of carbonaceous feedstock, thus protecting the limited capacity of fossil fuels.

The use of carbon dioxide as endothermic gasification agent such as an exhaust gas or obtained in the production of chemical products and in the combustion of carbon-containing energy carriers to generate energy, the carbon dioxide is recycled and re-converted to carbon being used materially and / or energetically. This reduces the emission of air-harmful carbon dioxide and leads to a closed carbon cycle.

At least another advantage of the invention is that existing systems can be additionally equipped with an electrolysis system. And thus, in the case of methane generation plant, their performance increases up to 400 % without additional coal or carbon materials and no additional gasification output.

In the following the invention is described in a preferred embodiment with reference to the appending drawing, in which Fig. 1 shows an embodiment of the invention with a schematic view on the arrangement and the method.

Fig. 1 shows an exemplary embodiment of the invention with a schematic view on the arrangement and the method. The arrangement comprises for the production of gaseous and / or liquid hydrocarbons 60, 61 from solid, liquid or gaseous carbonaceous fuel, waste and scrap or carbon carrier 1 :

an entrained flow gasifier 5 for the production of a carbon monoxide sustainable gasification gas 6,

a shift-process 22 to produce hydrogen 24 and carbon dioxide from carbon monoxide and water vapour,

a gas treatment and gas purification means 27 for removal of unwanted gas components 28 as well as carbon dioxide 29 and water 30 of the gasification gas, a mixed gas 26,

and

a synthesis process 43 for the production of gaseous and / or liquid hydrocarbons 44 from carbon monoxide and hydrogen, including means for removing the heat of reaction in form of water-vapour 48 and a water electrolysis 33, especially a steam electrolyser for hydrogen production 32.

Crushed and dried coal 1 is gasified with oxygen 2 and water vapour 3 and/or carbon dioxide 4 in an entrained flow gasifier 5 to gasification gas 6. The fuel ash contained in the coal 1 is discharged as slag 7 and the unreacted carbon as a residual carbon 8 is also discharged from the gasifier 5.

The coal quantity 1 is controlled by the quantity control device for carbon 9 and preheated in the electric heater 10 with excess capacity of renewable electric energy 1 1. The oxygen 2 can be pre-heated in the electric heater for oxygen 12 with excess capacity of renewable electric energy 13. Also the water vapour 3 can be pre-heated with the electric heater for oxygen 14 with excess capacity of renewable electric energy 15. The carbon dioxide 4 can also be pre-heated in the electric heater for carbon dioxide 16 with renewable electric energy 17.

The whole pre-heating processes will be only operated with renewable electric energy. The whole arrangement is constructed and optimized for the use of excess renewable electric energy. There will be no use of electricity from fossil fuels, so the purpose of protecting the environment takes effect. For cooling the gasification gas 6 quenching water 19 is injected into the gasification gas 6 at the gasifier outlet 18 of the entrained flow gasifier 5. Because of the cooling the cooled and water-vapour-saturated gasification gas 20 already contains much of the necessary amount of water vapour for the subsequent shift-process 22.

A branch stream of the water-vapour-saturated gasification gas to the shift-process 21 of the water-vapour-saturated gasification gas 20 is supplied to the shift process 22 for the conversion of carbon monoxide with water-vapour to hydrogen and carbon dioxide 24. A possibly required amount of additional water 23 can be supplied to the gas stream 21.

The hydrogen-packed gas 24 after the shift process 22 is mixed with the second portion of gas 25 from the gasifier outlet 18 and is supplied as a mixed gas 26 to the gas treatment and gas purification 27.

In the gas purification 27 all contaminations, such as sulfur and chlorine compounds, heavy metals, toxic elements 28 and carbon dioxide 29 and also the excess water 30 are removed in accordance with the requirements of the synthesis from the mixed gas 26.

Then the cleaned gas 31 is mixed with additional hydrogen 32 from the water electrolysis or the steam electrolyser 33, which is also operated with excess renewable electric energy 34, to synthesis gas 35. The hydrogen 32 from the water electrolysis 33 has been compressed in a hydrogen compressor 36 and temporarily stored in the hydrogen intermediate storage 37. The pressure in the hydrogen intermediate storage 37 is higher than the pressure in the gas generation process.

A gas analysis 38 is arranged in the gas stream. The gas analysis 38 determines the molar ratio of hydrogen to carbon monoxide in the synthesis gas 35. This molar ratio can be adjusted by changing the following variables:

- changing the amount of hydrogen 32 which is mixed into the gas from the hydrogen intermediate storage 37 by changing the flow rate with the hydrogen supply-regulation device 39, e.g. a valve. By changing the performance of the water electrolysis 34 the amount of hydrogen taken from the hydrogen

intermediate storage 37 will be compensated;

- adjustment of the bypass stream 25 which bypasses the shift process 22 by adjusting the bypass stream controller 40 to change the flow rate of the water- vapour-saturated gasification gas 25;

- changing the quantity ratio of the endothermic gasification agents water-vapour 3 and/or carbon dioxide 4 by adjusting the water vapour supply-regulation device 41 and/or the carbon dioxide supply-regulation device 42;

- changing the heating temperature of the endothermic gasification agents water- vapour 3 by adjusting the heating power (renewable electric energy) 15 to the electric heater for water vapour 14; - changing the heating temperature of the endothermic gasification agents carbon dioxide 4 by adjusting the heating power (renewable electric energy) 17 to the electric heater for carbon dioxide 16;

- changing the heating temperature of the oxygen 2 by adjusting the heating power (renewable electric energy) 13 to the electric heater for oxygen 12; - changing the heating temperature of the solid, liquid / gaseous carbon or carbon carrier 1 by adjusting the heating power (renewable electric energy) 1 1 to the electric heater for carbon 10; - changing the gasification performance by adjusting the carbon / coal feeding stream with the quantity control device for carbon 9;

The synthesis gas 35 is fed in the methane synthesis 43, in which the synthesis gas 35 is converted to methane 44 and water vapour / reaction water 45. The water vapour 45 is removed by cooling with a gas cooler 46 in the form of water vapour condensate 47. The water vapour condensate 47 from the methane 44 can be used as process water (for example as quenching water 19 or additional water for the shift-process 23).

The emitted heat of the synthesis process 43 is dissipated from the process in the form of pressure steam / water vapour 48 and is used as the gasification agent water vapour 3, as water vapour for the steam electrolyser 49 and/or as excess water vapour / steam 50 for other purposes.

The oxygen 51 produced in the water or steam electrolyser 33 together with the hydrogen 32 is stored in the oxygen intermediate storage 53 after being compressed by the oxygen compressor 52 and the optionally condensing in the oxygen liquefier 66. The stored oxygen 51 is subsequently used to bridge too small quantities of oxygen 51 from the steam electrolyser 33 for the gasification process. Excess oxygen produced in the steam electrolyser 54 must be discharged to the

atmosphere or must be stored or used in other ways. If the oxygen 51 produced in the steam electrolyser 33 is insufficient and there is not enough oxygen stored in the oxygen intermediate storage 53 additional oxygen 55 must be generated e.g. from an air separation plant (not shown) or the like.

The carbon dioxide 29 generated in the shift process 22 and separated in the gas purification 27 is compressed by the carbon dioxide compressor 57 and stored, according to the storage capacity, in the carbon dioxide intermediate storage 56.

Excess carbon dioxide 58 must be discharged to the atmosphere or be used in other ways. The carbon dioxide from the carbon dioxide intermediate storage 56 is used primarily during periods of excess renewable electric energy in the grid as an endothermic gasification agents 4 to increase the hydrogen absorption capacity of the gas produced in the entrained flow gasifier 5. Missing carbon dioxide 59 must be supplied to the process from the outside. The excess carbon dioxide 29 from the gas purification 27 and/or more carbon dioxide from external sources can be added additionally to the water vapor 49 to the steam electrolyser 33, which is adapted to decompose carbon dioxide into carbon monoxide and oxygen by the use of renewable electric energy. For increasing the production efficiency the carbon monoxide from the electrolysis 33 is added as a component to the synthesis gas 35 before the synthesis process 43.

Another embodiment of the invention for the production of carbon monoxide, hydrogen and oxygen is to use the gasification gas 6 or the water- vapor-saturated gasification gas 20 directly in the steam electrolyser 33 while using only excess renewable electric energy. In this procedure the carbon dioxide generated in the gasifier 5, the water vapor from the gasifier 5 and the quench water 19 are used in the electrolysis 33 to form carbon monoxide, hydrogen and oxygen.

The amount of methane 61 , additionally produced to the amount of methane 60, produced in addition to the integration of renewable electric energy 1 1 , 13, 15, 17 and (and/or) 34, only generated from renewable energy sources, may preferably be stored and transported in the natural gas grid 62. Afterwards an electricity regeneration in a suitable power generator or reconversion device 63 and feeding to the electricity grid 64 is possible. Furthermore, a different energy form is possible, for example as a fuel, or as an alternative material or energy-related use of methane 65.

Using the following examples and embodiments the different operating modes (variant 1 to 6) and the different effects will be explained by theoretical

considerations:

Variant 1 (prior art): For the prior art production of methane 60 from carbon 1 by gasification with oxygen 2 and water vapour 3 as gasification agents it is valid to set and control the required hydrogen - carbon monoxide - molar ratio by the production of hydrogen from carbon monoxide in a diverted stream of the branch stream of the water-vapour- saturated gasification gas 25 to the shift-process with the bypass stream controller 40 by the shift-process 22 (see: reactions R4 to R7). This prior art process of methane production is without the integration of renewable electric energy (1 1 , 13, 15, 17, 34). For the methane-production from coal / carbon with a molar ratio of H₂: CO = 3. If no renewable electric energy is available, this would be the possible operation mode. gasification: 3,3 C + 1 ,3 O₂ + 0,7 H₂O -» 3,3 CO + 0,7 H₂ (R4)

CO-shift: 2,3 CO + 2,3 H₂0 ^ 2,3 H₂ + 2,3 C0₂ (R5) synthesis: CO + 3 H₂ -» CH₄ + H₂0 (R6) total: 3,3 C + 1 ,3 0₂ + 2 H₂0 -» CH₄ + 2,3 C0₂ (R7)

The following variants 2 to 6 (B) arise with the new arrangement and the new method with the integration of renewable electric energy:

Variant 2: Reducing the shift process to 0 mol CO shift by bypassing the shift process 22 with the total gas stream 20 as the bypass stream 25; using the water vapour 3 with a temperature of 298 K as endothermic gasification agent (substance) and integration of the required amount of hydrogen 32 from a water vapour-electrolysis 33, which is operated only with excess renewable electric energy 34. The other possible options for using renewable electric energy (1 1 , 13, 15, 17) are not in operation. gasification: 3,3 C + 1 ,3 0₂ + 0,7 H₂0 -» 3,3 CO + 0,7 H₂ (R12) electrolysis: 9,2 H₂0 -» 9,2 H₂ + 4,6 0₂ (R13) synthesis: 3,3 CO + 9,9 H₂ -» 3,3 CH₄ + 3,3 H₂0 (R14) total: 3,3 C + 6,6 H₂0 -» 3,3 CH₄ + 3,3 0₂ (R15) Variant 3:

Reducing the shift process to 0 mol CO shift by bypassing the shift process 22 with the total gas stream 20 as the bypass stream 25; using the water vapour 3 (steam) as the endothermic gasification substance (agent), which is preheated only by excess renewable electric energy 15 in the electric heater for water vapour 14 to 1300 K and integration of the required amount of hydrogen 32 generated by the steam electrolyser 33, which is also operated only with excess renewable electric energy 34. The other possible options for using renewable electric energy (1 1 , 13, 17) are not in operation. gasification: 3,3 C + 1 ,25 0₂ + 0,81 Η₂0→· 3,3 CO + 0,81 H₂ (R16) electrolysis: 9, 1 H₂0 -» 9, 1 H₂ + 4,55 0₂ (R17) synthesis: 3,3 CO + 9,9 H₂ ^ 3,3 CH₄ + 3,3 H₂0 (R18) total: 3,3 C + 6,6 H₂0 -» 3,3 CH₄ + 3,3 0₂ (R19)

Variant 4:

Reducing the shift process to 0 mol CO shift by bypassing the shift process 22 with the total gas stream 20 as the bypass stream 25; using the carbon dioxide 4 with a temperature of 298 K instead of water vapour 3 as the endothermic gasification agent and integration of the required hydrogen amount 32 from the steam electrolyser 33, which is operated only with excess renewable electric energy 34. The other possible options for using renewable electric energy (1 1 , 13, 15, 17) are not in operation. gasification: 3,3 C + 1 ,35 0₂ + 0,61 C0₂ -» 3,91 CO (R20) electrolysis: 1 1 ,72 H₂0 -»1 1 ,72 H₂ + 5,86 0₂ ( 21 ) synthesis: 3,91 CO + 1 1 ,72 H₂ 3,91 CH₄ + 3,91 H₂0 (R22) total: 3,3 C + 0,61 C0₂ + 7,81 H₂0 -» 3,91 CH₄ + 4,51 0₂ (R23) Variant 5:

Reducing the shift process to 0 mol CO shift by bypassing the shift process 22 with the total gas stream 20 as the bypass stream 25; using the carbon dioxide 4 instead of water vapour 3 as the endothermic gasification agent, which is preheated to 1300 K in the heater for carbon dioxide 16 only with excess renewable electric energy 17, and integration of the required amount of hydrogen 32 from the steam electrolyser 33, which is operated only with excess renewable electric energy 34. The other possible options for using renewable electric energy (1 1 , 13, 15) are not in operation. gasification: 3,3 C + 1 ,3 0₂ + 0,71 C0₂ 4,01 CO (R24) electrolysis: 12,04 H₂0 12,04 H₂ + 6,02 0₂ (R25) synthesis: 4,01 CO + 12,04 H₂ ^ 4,01 CH₄ + 4,01 H₂0 (R26) total: 3,3 C + 0,71 C0₂ + 8,03 H₂0 ^ 4,01 CH₄ + 4,73 0₂ (R27)

Variant 6:

Reducing the shift process to 0 mol CO shift by bypassing the shift process 22 with the total gas stream 20 as the bypass stream 25; using the carbon dioxide 4 instead of water vapour 3 as the endothermic gasification agent, which is preheated to 1300 K in the electric heater for carbon dioxide 16 only with excess renewable electric energy 17.

Furthermore, the oxygen 2 is preheated in the heater for oxygen 12 and the coal / carbon 1 is preheated in the electric heater for carbon 10 only operated with excess renewable electric energy 13 respectively 1 1 to a temperature of 800K.

The required amount of hydrogen 32 is produced by the steam electrolyser 33, which is also operated only with excess renewable electric energy 34.

The other possible option for using renewable electric energy 15 is not in operation. gasification: 3,3 C + 1 ,21 O2 + 0,87 C0₂ -» 4,17 CO (R28) electrolysis: 12,52 H₂0 -» 12,52 H₂ + 6,26 0₂ (R29) synthesis: 4, 17 CO + 12,52 H₂ -» 4, 17 CH₄ + 4, 17 H₂0 (R30) total: 3,3 C + 0,87 C0₂ + 8,34 H₂0 -» 4, 17 CH₄ + 5,04 0₂ (R31 )

In the variants 2 to 6 (B) the shift-process 22 is turned off by bypassing the water- vapour-saturated gasification gas around the shift-process 22 through the use of the bypass stream 25. The performances of the water electrolysis (33) and/or the heating of carbon and/or the heating of oxygen and/or the heating of water vapour and/or the heating of carbon dioxide are controlled individually in the range from 0 to 100 %. A preferred embodiment is to combine the variants by controlling the performance individually in relation to the amount of excess renewable electric energy.

The results can be found in the following table with the relevant parameters and values for the individual variants (table 1 ):

Table 1 : parameter for the variants 1 to 6

List of reference numbers

1 solid, liquid / gaseous carbon or carbon carrier

2 oxygen

3 water vapour

4 carbon dioxide

5 entrained flow gasifier

6 gasification gas

7 slag

8 rest carbon

9 quantity control device for carbon

10 electric heater for carbon

1 1 renewable electric energy

12 electric heater for oxygen

13 renewable electric energy

14 electric heater for water vapour

15 renewable electric energy

16 electric heater for carbon dioxide

17 renewable electric energy

18 gasifier outlet

19 quenching water

20 water-vapour-saturated gasification gas

21 branch stream of the water-vapour-saturated gasification gas to the shift- process

22 shift-process

23 additional water for the shift-process

24 hydrogen-packed gas after the shift-process

25 bypass stream for the water-vapour-saturated gasification gas bypassing the shift-process

26 mixed gas

27 gas treatment and gas purification

28 toxic elements

29 carbon dioxide

30 excess water

31 cleaned gas

32 additional hydrogen from the water electrolysis

33 water electrolysis / steam electrolyser

34 renewable electric energy

35 synthesis gas

36 hydrogen compressor

37 hydrogen intermediate storage

38 gas analysis hydrogen supply-regulation device

bypass stream controller

water vapour supply-regulation device

carbon dioxide supply-regulation device

synthesis

methane

reaction water

gas cooler

water vapour condensate

water vapour, heat of reaction

water vapour for the water vapour-electrolysis

excess water vapour

oxygen produced in the electrolysis

oxygen compressor

oxygen intermediate storage

excess oxygen produced in the electrolysis

added oxygen by an external air separation device

carbon dioxide intermediate storage

carbon dioxide compressor

excess carbon dioxide

added carbon dioxide

methane produced while operating in variant 1 without the use of renewable electric energy

additional produced methane by use of renewable electric energy natural gas grid

reconversion device

electricity grid

alternative material or energy-related use of methane

oxygen liquefier

Claims

C L A I M S

A hydrocarbon-production-apparatus for the production of gaseous and / or liquid hydrocarbons (44, 60, 61 ) from solid, liquid or gaseous carbonaceous carrier (1 ) comprising:

- a gasifier (5) for the production of a gasification gas (6) containing carbon monoxide,

- a shift-process (22) to produce hydrogen and carbon dioxide from carbon monoxide and water vapour,

and

- a synthesis process (43) for the production of gaseous and / or liquid hydrocarbons (44) from carbon monoxide and hydrogen,

characterized by

- a bypass stream (25) for the gasification gas (6, 20) to bypass the shift- process (22)

and

- a water electrolysis (33) operable only with renewable electric energy (34) for hydrogen production.

The hydrocarbon-production-apparatus of claim 1 ,

wherein the apparatus comprises at least one electric heater (10, 12, 14, 16) operable only with renewable electric energy ( 1 1 , 13, 15, 17) to heat carbon, oxygen, water vapour and/or carbon dioxide.

The hydrocarbon-production-apparatus of claim 2,

wherein the apparatus comprises four electric heater (10, 12, 14, 16) operable only with renewable electric energy ( 1 1 , 13, 15, 17) to heat carbon (10), oxygen (12), water vapour (14) and carbon dioxide (16).

The hydrocarbon-production-apparatus of claim 1 , 2 or 3,

wherein the water electrolysis (33) is a steam electrolyser (33).

5. The hydrocarbon-production-apparatus of claim 1 , 2, 3 or 4,

wherein the gasifier (5) is an entrained flow gasifier (5). The hydrocarbon-production-apparatus of claim 1 , 2, 3, 4 or 5,

wherein the apparatus comprises a gas treatment and gas purification means (27) for removal of unwanted gas components (28), carbon dioxide (29) and water (30) from the gasification gas (6).

The hydrocarbon-production-apparatus of claim 1 , 2, 3, 4, 5 or 6, wherein the synthesis process (43) includes means for removing the heat of reaction in form of water vapour (48) for re-using the water vapour (48) in the steam electrolyser (33) and/or as excess water vapour for other purposes and/or as the endothermic gasification agent (3).

A hydrocarbon-production-method with a hydrocarbon-production-apparatus according to any one of claims 1 to 7,

comprising at least two processing-variants with steps:

wherein

- in the first variant (A):

the shift-process (22) produces hydrogen and carbon dioxide from carbon monoxide and water vapour

and

- in the second variant (B):

- the shift-process (22) is turned off by bypassing the water-vapour- saturated gasification gas around the shift-process (22) through the use of the bypass stream (25) and

- the water electrolysis (33) produces hydrogen with renewable electric energy (34),

wherein the second variant (B) is executed only if excess renewable electric energy (34) is available.

The hydrocarbon-production-method of claim 8, wherein the first variant (A) and the second variant (B) are operated simultaneously if the second variant (B) is executable.

The hydrocarbon-production-method of claim 8 or 9, wherein extra renewable electric energy (1 1 , 13, 15, 17) is additionally used in the second variant (B) for heating carbon, oxygen, water vapour and/or carbon dioxide. The hydrocarbon-production-method of claim 8, 9 or 10, wherein carbon dioxide is used as an endothermic gasification agent for the gasification in the second variant (B), wherein said carbon dioxide was generated preferably in the shift-process (22) and buffered in an intermediate storage (56) in times when there was not enough excess renewable electric energy available.

12. The hydrocarbon-production-method of claim 8, 9, 10 or 1 1 , wherein oxygen, being generated in the electrolysis (33) with excess renewable electric energy, is used as a gasification agent for the gasification. 13. The hydrocarbon-production-method of claim 8, 9, 10, 1 1 or 12, wherein the performances of the water electrolysis or steam electrolyser (33) and/or the heating of carbon and/or the heating of oxygen and/or the heating of water vapour and/or the heating of carbon dioxide are controlled individually in the range from 0 to 100 %.

The hydrocarbon-production-method of claim 8, 9, 10, 1 1 , 12 or 13, wherein excess carbon dioxide (29) from a gas purification (27) and/or more carbon dioxide from external sources is added additionally to water vapor (49) to the steam electrolyser (33), which is adapted also to decompose carbon dioxide into carbon monoxide and oxygen by the use of excess renewable electric energy.

The hydrocarbon-production-method of claim 8, 9, 10, 1 1 , 12, 13 or 14, wherein the gasification gas (6) or the water- vapor-saturated gasification gas (20) is used directly in the steam electrolyser (33) for the production of carbon monoxide, hydrogen and oxygen while using only excess renewable electric energy.