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    • 专利摘要:
    METHOD FOR GENERATING SYNTHESIS GAS, METHOD FOR GENERATING SYNTHETIC HYDROCARBONS AND / OR NOT FUNCTIONING, APPLIANCE FOR GENERATING SYNTHESIS GAS / SYNTHESIS AND SYNTHETIC GAS. A method and apparatus for generating synthesis gas using hydrocarbons and water are described. In additional method and apparatus modalities, synthesis gases having any desired ratio of CO / hydrogen and / or functionalized and / or non-functionalized synthetic hydrocarbons are generated. With this method, a hydrocarbon-containing fluid can be transformed into a synthesis gas having a variable hydrogen content without generating significant amounts of CO2. In addition, hydrogen and different forms of carbon can be obtained as by-products.
    公开号:BR112014014984B1
    申请号:R112014014984-4
    申请日:2012-12-20
    公开日:2020-11-17
    发明作者:Olaf Kühl
    申请人:CCP Technology GmbH；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process and a system for generating synthesis gas from hydrocarbons and water.
    [0002] Significant parts of the world economy are based on crude oil as a raw material or as a source of energy. In this way, Otto and Diesel fuel for individual and goods transport, heavy oil for ships and as fuel for electric power plants as well as light oil for heating family homes are produced from crude oil. In addition, many raw materials for the chemical industry are derived, directly or indirectly, from crude oil. At the moment, significant efforts are being made to replace crude oil derivatives with other raw materials or alternative processes. In an energy sector, natural gas and renewable energy are used instead of crude oil in the operation of power plants. Electric engines, natural gas engines and hydrogen fuel cells are tested for traffic applications, but could not be commercially established.
    [0003] There are attempts to produce petroleum products from natural gas or coal on an industrial scale. For example, processes for transforming natural gas into liquid fuels are known (so-called gas-liquid processes or GTL). However, these processes generally involve significant CO2 emissions and high costs. In addition, they are not usually able to supply hydrogen regardless of CO or C02. Therefore, these attempts are usually limited, due to economic and ecological reasons, to some isolated applications.
    [0004] Synthesis gas, or abbreviated syngas, is a mixture of carbon monoxide and hydrogen gas that can also contain carbon dioxide. For example, syngas is generated by gasifying fuel containing carbon in a gaseous product, syngas, having a certain calorific value. Synthesis gas has approximately 50% of the energy density of natural gas. The synthesis gas can be burned and thus used as a fuel source. Synthesis gas can also be used as an intermediate product in the generation of other chemicals. For example, synthesis gas can be generated by gasifying coal or waste. In the generation of synthesis gas, carbon can react with water, or a hydrocarbon can react with oxygen. There are commercially available technologies for processing synthesis gas to generate industrial gases, fertilizers, chemicals and other chemicals. However, better known technologies (for example, water displacement reaction) for the generation and transformation of synthesis gas have the problem that synthesis of the required amount of hydrogen causes the generation of a larger amount of excess CO2 which is finally emitted to the atmosphere as a harmful climate gas. Another known technology for the production of synthesis gas, the partial oxidation of methane according to the equation 2 CH4 + O2 -> 2 CO + 4 Ü2 can reach the maximum HSIC ratio of 2.0. However, the disadvantage is the use of pure oxygen, which is the energy intensively produced.
    [0005] Therefore, a first problem to be solved by the invention is to transform a fluid containing hydrocarbon into synthesis gas with a variable hydrogen content, without generating significant amounts of CO2.
    [0006] The problem is solved by methods according to claims 1, 14 and 15 as well as by the apparatus according to claims 19 and 28. Additional modalities can be derived from the dependent claims.
    [0007] In particular, a method for generating synthesis gas comprises decomposing a hydrocarbon-containing fluid into carbon and hydrogen by introducing energy that is at least partially provided by heating, wherein the carbon and hydrogen have a temperature of at least at least 200 ° C after the decomposition step. A portion of the carbon generated by the decomposition step is then placed in contact with the water at a temperature between 800 and 1700 ° C, where the carbon generated by the decomposition step cools no more than 50% in ° C with respect to its temperature after the decomposition step by placing the carbon in contact with the water. In this document, at least a portion of the water, together with the carbon generated by the separation process, is transformed into synthetic gas. This method allows the transformation of a hydrocarbon-containing fluid into synthesis gas having a variable hydrogen content, without generating significant amounts of CO2. Advantageously, at least part of the energy required to supply carbon (by separating a hydrocarbon), is introduced in the form of heating for transformation. Additionally, hydrogen and different varieties of carbon can be produced as by-products.
    [0008] This is particularly true if the decomposition step takes place at a temperature over 1000 ° C and the carbon is brought into contact with water at a temperature of at least 1000 ° C, particularly at a temperature between 1000 ° C and 1200 ° C, since in this case none or a small amount of additional need to be supplied for the transformation. Preferably, the heating required to reach the temperature of 800 to 1700 ° C (particularly from 1000 ° C to 1200 ° C) for the transformation is essentially completely provided by the heating which is used for the separation of the hydrocarbon-containing fluid. In the present document, essentially completely means that at least 80%, specifically at least 90% of the required heating comes from the decomposition step.
    [0009] In one embodiment, the carbon obtained in the decomposition stage and the hydrogen obtained in the decomposition stage are both placed in contact with water. Hydrogen does not compromise the transformation and can serve as an additional heat transfer substance. This is particularly advantageous if the carbon and hydrogen have a temperature of 1000 ° C (a preferred transformation temperature) or above. In this case, the gas after transformation is not pure water gas, but a synthesis gas with a different mixing ratio.
    [0010] Alternatively, the carbon obtained from the decomposition step can be separated from the hydrogen obtained from the decomposition step before the step of putting the carbon in contact with water.
    [0011] In order to increase the energy efficiency of the method, at least a portion of the heating of at least a portion of the carbon and / or a portion of the hydrogen obtained from the decomposition step, can be used to heat the water before the step of putting the water in contact with the carbon and / or it can be used to heat the process chamber, in which the water is placed in contact with the carbon. In this sense, it should be noted that the synthesis gas has a temperature of 800 to 1700 ° C after transformation and that at least part of its heat can be used to preheat the water before the step of putting the water in contact with carbon. It is also possible that at least part of the heat from at least a portion of the carbon and / or hydrogen obtained from the decomposition step, and / or a portion of the synthesis gas after transformation can be used to generate electricity that can be used as an energy carrier to introduce energy to the hydrocarbon-containing fluid decomposition step.
    [0012] Preferably, the energy to decompose the hydrocarbon is primarily introduced via plasma. This is a particularly straightforward and therefore efficient method of introducing energy. Preferably, the decomposition step is carried out in a Kvaerner reactor that allows the continuous decomposition of a hydrocarbon stream.
    [0013] In the method for generating a synthesis gas, additional hydrogen and / or carbon monoxide and / or even synthesis gas can be added to the synthesis gas in order to obtain a desired composition. In the case of bringing both carbon and hydrogen into contact with water, it may be particularly useful to add additional carbon monoxide to the synthesis gas in order to reduce the CO / H2 ratio. During the stage of essentially putting pure carbon in contact with water, it may be useful to add additional carbon monoxide to increase the CO / H2 ratio. In particular, it is possible to mix the flows of two synthesis gases generated separately according to the aforementioned method (with and without the previous separation of carbon and hydrogen) in order to obtain a desired ratio of the mixture of CO / H2.
    [0014] Preferably, the additional hydrogen originates from the step of decomposing a fluid containing hydrocarbon into carbon and hydrogen by introducing energy that is at least partially accomplished by heat. Therefore, the decomposition step can provide the carbon needed for the carbon-water and hydrogen transformation needed in one step. In one embodiment, at least a portion of the hydrogen is generated by the step of decomposing a fluid containing hydrocarbon at a temperature below 1000 ° C, specifically below 600 ° C, by means of a microwave plasma. Where additional hydrogen (more than the amount that is obtained by producing the carbon necessary for the carbon-water transformation) is required to obtain a specific mixing ratio for a synthesis gas, it is preferred to generate said hydrogen in an efficient way. energy at low temperatures from a hydrocarbon-containing fluid. Preferably, the ratio of CO to hydrogen in the synthesis gas is adjusted to a value between 1: 1 and 1: 3, specifically to a value of 1: 2.1.
    [0015] In a method to generate functionalized and / or non-functionalized synthetic hydrocarbons, in a first step, a synthesis gas is generated, as described above, and the synthesis gas is brought into contact with a suitable catalyst in order to cause transformation of the synthesis gas into functionalized and / or non-functionalized synthetic hydrocarbons, where the temperature of the catalyst and / or the synthesis gas is established or regulated to a predefined temperature range. In this way, the synthesis gas can be generated by mixing CO with hydrogen, either before or when placed in contact with the catalyst.
    [0016] In one embodiment, the transformation of the synthesis gas is carried out by a Fischer-Tropsch process, specifically an SMDS process. Alternatively, the synthesis gas transformation can be carried out by a Bergius-Pier process, a Pier process or a combination of a Pier process with a MtL process. It is the choice of the process, which largely determines the nature of functionalized and / or non-functionalized synthetic hydrocarbons.
    [0017] Preferably, the hydrocarbon-containing fluid to be decomposed is natural gas, methane, wet gas, heavy oil, or a mixture of these.
    [0018] The apparatus for generating synthetic gas comprises a hydrocarbon converter for decomposing a fluid containing hydrocarbon into carbon and hydrogen, wherein the hydrocarbon converter comprises at least one process chamber having at least one inlet for a fluid containing hydrocarbon and at least one outlet for carbon and / or hydrogen and at least one unit for introducing energy into the process chamber, the energy at least partially consisting of heat. The apparatus further comprises a C converter for the transformation of water and carbon, the C converter comprising at least one additional process chamber having at least one inlet for water, at least one inlet for at least carbon and at least one output, where the input for at least carbon is directly connected to at least one output of the hydrocarbon converter. In this document, the term "directly connected" describes that the carbon leaving the hydrocarbon converter does not cool more than 50% of its temperature in ° C, preferably not more than 20%, on its way to the C converter without the use of additional energy to heat the carbon. A separate unit, which separates carbon from hydrogen, can be provided between the location of the decomposition step and at least one outlet of the hydrocarbon converter. This unit can form part of the hydrocarbon converter or it can be located outside the hydrocarbon converter as a separate unit. A separate unit between the output of the hydrocarbon converter and the input of a C converter does not compromise a direct connection as long as the above condition is satisfied.
    [0019] Preferably, at least one unit to introduce energy into the process chamber is constructed in such a way that it is capable of at least locally generating temperatures above 1000 ° C, specifically above 1500 ° C. In one embodiment, at least one unit for introducing energy into the process chamber is a plasma unit. Particularly, if the decomposition temperature is to be kept below 1000 ° C, that at least one unit for introducing energy into the process chamber preferably comprises a microwave plasma unit.
    [0020] For a particularly simple modality of the device, the process chamber of the C converter is formed by a hydrocarbon converter outlet pipe that is connected to a water supply pipe.
    [0021] In an embodiment of the invention, a separation unit to separate the carbon and hydrogen generated by the decomposition is provided in the vicinity of the hydrocarbon converter, and separate outlets from the separation unit are provided for the separate materials, in which the outlet for carbon is connected to the C converter.
    [0022] Preferably, the hydrocarbon converter is a Kvaerner reactor that can provide the temperature necessary for a continuous separation of a hydrocarbon-containing fluid for long periods of operation.
    [0023] For a simple and efficient generation of a synthesis gas having a variable mixing ratio, the apparatus may comprise at least one separate supply tube for the supply of hydrogen and / or carbon and / or a separate synthesis gas in the C converter or a downstream mixing chamber.
    [0024] In one embodiment, the apparatus for generating synthesis gas comprises at least one additional hydrocarbon converter to decompose a fluid containing hydrocarbon into carbon and hydrogen. At least one additional hydrocarbon converter again comprises at least one process chamber having at least one hydrocarbon-containing fluid inlet, at least one unit for introducing energy into the process chamber, where the energy at least partially consists of heat, and a separation unit to separate carbon from hydrogen, which were obtained by decomposition, the separation unit having separate outlets for carbon and hydrogen, in which the outlet for hydrogen is connected to a separate supply tube for hydrogen. For reasons of energy efficiency, at least one additional hydrocarbon converter is preferably of the type that performs the decomposition at temperatures below 1000 ° C, specifically below 600 ° C, by means of a microwave plasma.
    [0025] The apparatus for transforming a synthesis gas into functionalized and / or non-functionalized synthetic hydrocarbons comprises an apparatus for generating synthesis gas of the type specified above and a CO converter. The CO converter comprises the process chamber equipped with a catalyst, means for bringing the synthesis gas into contact with the catalyst, and a control unit for controlling or regulating the temperature of the catalyst and / or the synthesis gas to a temperature predetermined. In this way, parts of the apparatus for generating a synthesis gas can be integrated into the CO converter, for example, the mixing chamber for additional CO and hydrogen, carbon and / or another synthesis gas. In one embodiment, the CO converter comprises a Fischer-Tropsch converter, particularly an SMDS converter. Alternatively, the CO converter can comprise a Bergius-Pier converter, a Pier converter or a combination of a Pier converter and a MtL converter. It is also possible that several CO converters of the same or different types are present in the device.
    [0026] Preferably, the apparatus comprises a control unit for controlling or regulating the pressure of the synthesis gas inside the CO converter.
    [0027] Below the invention is explained in more detail with reference to certain modalities and drawings, in which
    [0028] Fig. 1 is a schematic representation of a plant to generate synthesis gas;
    [0029] Fig. 2 is a schematic representation of an alternative plant to generate synthesis gas;
    [0030] Fig. 3 is a schematic representation of a plant to generate functionalized and / or non-functionalized hydrocarbons;
    [0031] Fig. 4 is a schematic representation of another plant to generate functionalized and / or non-functionalized hydrocarbons according to another modality;
    [0032] Fig. 5 is a schematic representation of a plant to generate functionalized and / or non-functionalized hydrocarbons according to another modality;
    [0033] Fig. 6 is a schematic representation of a plant to generate functionalized and / or non-functionalized hydrocarbons according to another modality;
    [0034] Fig. 7 is a schematic representation of a plant to generate synthetic gas according to another modality; and
    [0035] Fig. 8 is a schematic representation of a plant to generate functionalized and / or non-functionalized hydrocarbons according to another modality.
    [0036] It should be noted the terms top, bottom, right and left as well as similar terms in the description below refer to the guidelines and arrangements, respectively, shown in the figures and are only intended to describe the modalities. These terms may show, but are not limited to, preferred arrangements. In addition, in the different figures, the same reference numbers are used to describe the same or similar parts.
    [0037] In the following specification, processes and devices are described as dealing with "hot" materials or performing "hot" processes. Within the context of this description, the term "hot" should describe a temperature above 200 ° C and preferably above 300 ° C.
    [0038] Synthesis gas is any gas that consists mainly of carbon monoxide and hydrogen. A (synthetic) gas that consists of almost equal parts of carbon monoxide and hydrogen (1: 1), is called water gas. The term synthetic gas, as used herein, encompasses water gas as a special mixture of synthetic gas.
    [0039] Fig. 1 schematically shows a plant 1 for generating synthesis gas. Fig. 1 also clarifies the basic steps of the process for generating the syngas according to this description.
    [0040] Plant 1 for generating synthesis gas comprises a hydrocarbon converter 3 comprising a hydrocarbon inlet 4 and a first carbon outlet 5, an optional hydrogen outlet 6 as well as an optional second carbon outlet 7. Plant 1 for the generation of syngas still comprises a C 9 converter having a water inlet 10, a carbon outlet 11 (also referred to as inlet C) and a syngas outlet 12 (syngas outlet ). The hydrocarbon converter 3 and the C 9 converter are arranged so that the carbon output 5 of the hydrocarbon converter 3 is connected to the carbon input 11 of the C 9 converter via a direct connection 8, where the output 5 can directly define the carbon input 11 of the C 9 converter. In this way, the carbon can be transported directly from the hydrocarbon converter 3 into the C 9 converter.
    [0041] Hydrocarbon converter 3 is any hydrocarbon converter that can transform or decompose hydrocarbons introduced into carbon and hydrogen. The hydrocarbon converter 3 comprises the process chamber having an inlet for a hydrocarbon-containing fluid, at least one unit for introducing the decomposition energy into the fluid and at least one outlet. Decomposition energy is provided at least partially by heat, which is, for example, supplied by a plasma. However, the energy of the decomposition can also be provided by other means and, if the decomposition is primarily effected by heat, the fluid must be heated up to above 1000 ° C and particularly to a temperature above 1500 ° C.
    [0042] In the described mode, a Kvaerner reactor is used, which provides the required heating by means of a plasma arc. However, other reactors are known to operate at lower temperatures, particularly below 1000 ° C, and introduce additional energy in addition to heat into the hydrocarbon, for example, by means of a microwave plasma. As is further explained below, the invention considers both types of reactors (and also those operating without plasma), in particular also both types of reactors in combination with each other. Hydrocarbon converters that operate at a temperature above 1000 ° C are referred to as high temperature reactors, while those converters that operate at temperatures below 1000 ° C, particularly at temperatures between 200 ° C and 1000 ° C, are referred to as low temperature reactors.
    [0043] Within the hydrocarbon converter, hydrocarbons (CnHm) are decomposed into hydrogen and carbon by means of heating and / or a plasma. These hydrocarbons are preferably introduced into the reactor as gases. Hydrocarbons that are liquid under standard conditions can be vaporized prior to introduction into the reactor or can be introduced as micro-drops. Both forms are denoted as the following fluids.
    [0044] The decomposition of hydrocarbons should be done, if possible, in the absence of oxygen in order to avoid the formation of carbon oxides or water. However, small amounts of oxygen, which could be introduced along with hydrocarbons, are not harmful to the process.
    [0045] The Kvaerner reactor, described above, decomposes a fluid containing hydrocarbons in a plasma burner at high temperatures into pure carbon (for example, as activated carbon, carbon black, graphite or industrial soot) and hydrogen and possibly impurities . The hydrocarbon-containing fluid used as a raw material for hydrocarbon converter 3 are, for example, methane, natural gas, biogas, wet gases or heavy oil. However, functionalized and / or non-functionalized synthetic hydrocarbons can also be used as a raw material for hydrocarbon converter 3. After the initial decomposition step, the elements are usually present as a mixture, particularly in the form of an aerosol. This mixture can, as described below, be introduced into another process in this form or the mixture can be separated into its individual elements in a separation unit, which is not shown. In the context of this patent application, such a separation unit is considered to be part of the hydrocarbon converter 3, although the separation unit can be built as a separate unit. If no separation unit is provided, the carbon outlet 5 is the only outlet from the hydrocarbon converter 3 and directs the mixture (an aerosol) of carbon and hydrogen directly into the C 9 converter. If the separation unit is provided, the carbon, which is at least partially separated from hydrogen, can be directed into the C 9 converter using the carbon 5 outlet. The separate hydrogen and possibly additional carbon can be discharged via the optional 6 and 7 outlets.
    [0046] The C 9 converter can be any suitable C converter that can generate synthesis gas (syngas) from carbon (C) and water (H2O). In the modality of Fig. 1, inside the C 9 converter, H2O is passed over the flow of carbon or water is introduced in a flow of carbon and hydrogen and is mixed with the flow in order to be transformed according to the equation chemistry C + H2O -► CO + H2. In the C 9 converter, the following reactions occur: + c + H2O -> • co + H2 131.38 kJ / mol endotherm CO + H2O -> CO2 + H2 - 41.19 kJ / mol exotherm
    [0047] In the Boudouard equilibrium, it occurs in the following reaction: 2 C + 02 - 2 CO + 172.58 kJ / mol endotherm
    [0048] Since all three reactions are in equilibrium with each other, the process in the C 9 converter occurs preferably at high temperatures of 800 to 1700 ° C, preferred from 1000 to 1200 ° C, since the The second reaction would be dominant at lower temperatures, where the heating required to reach the above temperature is primarily provided by the material emitted from hydrocarbon converter 3, as is described in more detail below. Under these conditions, the water (H2O) in the C 9 converter is steam, and the water can already be introduced as steam. The water supply during operation is controlled so that an excess of water is avoided, in order to avoid strong cooling. In case of excess cooling in the C 9 converter, reaction 2 above would also be dominant.
    [0049] The CO2 converter 9 operates better at high temperatures from 1000 to 1200 ° C in order to suppress the exothermic water displacement reaction CO + H2O -> • CO2 + H2 and thus optimize the sharing of carbon monoxide in the synthesis gas. The reactions in the C 9 converter are known to the person skilled in the art and are therefore not discussed in more detail in this document.
    [0050] The operation of plant 1 for the generation of synthesis gas is described in more detail below, with reference to Fig. 1. Next, it is assumed that the hydrocarbon converter 3 is a high temperature reactor of the Kvaerner type. Hydrocarbon-containing fluids (specifically in gaseous form) are introduced into hydrocarbon converter 3 via hydrocarbon inlet 4. If the hydrocarbon is, for example, methane (CH4), then 1 mol of carbon and 2 mol of hydrogen are generated from of 1 mol of methane. The hydrocarbons are transformed at about 1600 ° C in the plasma torch of the hydrocarbon converter 3 according to the reaction equation below, in which the energy introduced is heat that is generated in the plasma by means of electrical energy: CnHm + Energy -> n C + m / 2 H2
    [0051] With the proper process control, the Kvaerner reactor is capable of transforming almost 100% of the hydrocarbons in its components in a continuous operation.
    [0052] Next, it is assumed that the carbon and hydrogen are separated in hydrocarbon converter 3 and are discharged widely apart. However, it is also possible that the separation does not occur, but carbon and hydrogen are discharged and introduced into the C 9 converter as a mixture. Hydrogen does not compromise the transformation process in the C 9 converter, but it can serve as an additional heat transfer substance. The carbon is at least partially directed directly from the carbon outlet 5 to the carbon inlet 11 of the C 9 converter. The term "direct" directing from outlet 5 of the hydrocarbon converter 3 to the carbon inlet 11 of the C 9 converter. it must include all variants that do not experience cooling of more than 50% of the temperature (preferably not more than 20%) of the targeted materials. Since the carbon leaving the hydrocarbon converter 3 has a high temperature, preferably more than 1000 ° C, the thermal energy contained therein can be used to maintain the temperature required for the transformation process in the C 9 converter, which operates at a temperature of, for example, about 1000 ° C.
    [0053] Connection 8 between the hydrocarbon converter 3 and the C 9 converter is designed so that the carbon does not cool much (less than 50%, preferably less than 20% with reference to temperature) on its way from from hydrocarbon converter 3 to C converter 9. For example, connection 8 can be specially insulated and / or actively heated, where the system is preferably not provided with additional heating - that is, no additional heating is introduced in the hydrocarbon converter 3. The hydrogen that is generated in hydrocarbon converter 3, also contains thermal energy, because of the operating temperature in hydrocarbon converter 3. Therefore, a possibility to heat connection 8 is to use the thermal energy of the hydrogen that comes out through the hydrogen outlet 6, to heat the connection 8 between the hydrocarbon converter 3 and the C 9 converter or directly or indirectly via a heat exchange unit.
    [0054] In the C converter, water, particularly in the form of steam that is introduced through the water inlet 10 of the C 9 converter, is directed over the hot carbon and / or is mixed with the hot carbon. The C converter works best at high temperatures, since it is an endothermic reaction and the concurrent water displacement reaction is an exothermic reaction. The reaction, which is known to a person skilled in the art, depends on pressure and temperature and will not be described in detail. Either the amount of water introduced into the C 9 converter or the amount of carbon can be controlled (open circuit) and / or regulated (closed circuit) by suitable means. 0 + H2O - CO + H2; ΔH = + 131.38 kJ / mol
    [0055] Also in this document, the Boudouard balance is the limiting factor. That is because at temperatures above 1000 ° C and in the absence of a surplus of water, the mixture consists almost exclusively of carbon monoxide and hydrogen. It is advantageous to preheat the water introduced into the water inlet 10 of the C 9 converter, as the C 9 converter operates preferably at temperatures> 1000 ° C. For example, water preheating can be achieved using the thermal energy contained in the hot hydrogen or directly or indirectly via a heat exchange unit to preheat the water. Preferably, the heat contained in the carbon is sufficient to heat the water to the desired temperature. Only in the case where the heat generated in the hydrocarbon converter 3 is not sufficient to reach the desired transformation temperature of about 1000 ° C, an optional additional heating unit to heat the C 9 converter or the elements contained therein . Such a unit can also be supplied as a preheating unit in the vicinity of a water or carbon supply line. Such a unit can also be provided only for the start-up phase of the plant in order to bring the C 9 converter or media containing parts of the plants to a starting temperature so that the system can more quickly reach the desired temperature state . Heating of media containing parts exclusively via the heat generated in the hydrocarbon converter 3 may take too long at first.
    [0056] The hot synthesis gas (CO + H2) leaves the C 9 converter at a temperature of> 1000 ° C (depending on the operating temperature of the C 9 converter). The synthesis gas coming out of the C 9 converter also contains thermal energy, which can be used, for example, to preheat water introduced into a water inlet 10, or directly or indirectly via a heat exchange unit (not shown) in Fig. 1). With the proper operating parameters, this is a temperature between 1000 and 1200 ° C (and the separation of hydrogen and carbon in the hydrocarbon converter 3), a synthesis gas is generated, where CO and H2 have a ratio of 1: 1, which is called water gas. Without the separation of hydrogen and carbon in the hydrocarbon converter 3 and without the corresponding suitable operating parameters in the C 9 converter, that is, a temperature between 1000 ° C and 1200 ° C, a synthesis gas having a CO / H2 ratio of approximately 1: 3 will be produced.
    [0057] As mentioned above, the hydrocarbon converter 3 can comprise a second carbon outlet 7 for discharging carbon. The carbon generated in the hydrocarbon converter 3 can be discharged - after a respective separation (or as a C-H2 mixture) - in different proportions through the first carbon outlet 5 and the second carbon outlet 7. The second carbon outlet 7 is used to discharge a portion of the generated carbon that is not used in the C 9 converter to generate synthesis gas. The amount of unused carbon depends on the desired composition of the synthesis gas to be discharged from the C 9 converter. The carbon discharged through the second carbon outlet 7 can be discharged as activated carbon, graphite, carbon black or a another modification such as carbon cones or carbon discs. Depending on the shape and quality of the discharged carbon, the discharged carbon can be used as a raw material for the chemical industry or the electronics industry. Possible applications are, for example, the manufacture of semiconductors, the production of tires, paints, toner or similar products. The carbon generated by the hydrocarbon converter 3 is a highly pure raw material that can be very well processed.
    [0058] Using the method described above to generate synthesis gas, it is possible to convert the hot carbon from hydrocarbon converter 3 into the C 9 converter with warm or hot water into synthesis gas without or at least without significant external energy supply . Preferably, at least 80%, specifically at least 90%, of the heat required to reach the transformation temperature should originate from the hydrocarbon converter 3.
    [0059] Fig. 2 shows a plant 20 for the generation of synthesis gas comprising the elements described above from plant 1 for generating synthesis gas and the mixing chamber 21, the mixing chamber 21 comprising a gas inlet. synthesis 22 to introduce synthesis gas and an H2 inlet 23 to introduce hydrogen as well as a synthesis gas outlet 24 to discharge synthesis gas. The synthesis gas inlet 22 is connected to the synthesis gas outlet 12 of the C 9 converter. The H2 inlet 23 of the mixing chamber 21 is connected to the H2 6 outlet of the hydrocarbon converter 3. As is obvious for the technical person, the modality, which introduces a C-H2 mixture into the C 9 converter through the carbon outlet 5, automatically generates a synthesis gas having a CO-H2 mixing ratio of about 1: 3. In such a case, the mixing chamber 21 may not be present, or the mixing chamber 21 may be used to produce a different mixing ratio, or CO may be introduced into the mixing chamber in order to reduce the H2 content of the gas. of synthesis.
    [0060] The mixing chamber 21 can be any device suitable for mixing gases, and in a simple case the mixing chamber 21 can be in the form of a tube with suitable inlets and an outlet. Through the mixing chamber 21 and specifically through control / regulation (open / closed circuit) the amount of hydrogen (additional) introduced through the H2 input 23 of the mixing unit 21 and / or through an input (not shown) ) connected to a source of CO (not shown) and / or connected to a second source of synthesis gas, the mixture of the synthesis gas at the synthesis gas outlet 24 can be influenced so that a composition can be achieved, which it is suitable for subsequent processes. In particular, the second source of synthesis gas can be a second C 9 converter operated in parallel to a first C converter. Both C 9 converters could be fed with carbon and / or hydrogen from a shared hydrocarbon converter 3 or separate converter units. In particular, a first converter can be supplied substantially with pure carbon (after separating the hydrogen), and the second converter can be supplied with a mixture of carbon and hydrogen. In the present document, the first C converter would produce substantially water gas having a CO: H2 mixing ratio of about. 1: 1 and the second C converter would produce a synthesis gas having a CO: H2 mixing ratio of about 1: 3. Combining these two synthesis gases would produce a CO: H2 mixing ratio of about 1: 2, in which excess hydrogen (from a separation step prior to introduction into the first C converter) would still be available for the increase additional mixing ratio.
    [0061] For many processes, for example, Fischer-Tropsch synthesis, the hydrogen to CO ratio must be high. By means of the mixing chamber 21, any desired ratio of hydrogen to CO can be achieved at the exit of synthesis gas 24, for example, the ratio of 1: 1, which corresponds to water gas. It is considered that only a portion of the syngas and / or a portion of the hydrogen is supplied to the mixing chamber 21, while those portions of the syngas and hydrogen that are not introduced into the mixing chamber are each discharged of the process as pure gases. Therefore, it is possible, for example, to a) discharge only synthesis gas, b) discharge only hydrogen, c) discharge a synthesis gas mixture of CO and hydrogen or d) discharge a flow of water gas, a flow of hydrogen and a flow of a mixture of syngas (any ratio between CO and hydrogen) or several syngas with different ratios between carbon monoxide and hydrogen, respectively.
    [0062] In addition, the plant 20 for generating synthesis gas in Fig. 2 comprises a C 25 heat exchange unit, a synthesis gas heat exchange unit 26 and an H2 heat exchange unit 27. The C 25 heat exchange unit is in thermally conductive contact with connection 8 between the hydrocarbon converter 3 and the C 9 converter and is adapted to, if necessary, extract the excess heat not required to reach the temperature transformation in the C 9 converter from the connection or introduce heat from other areas of the plant, if necessary.
    [0063] The synthesis gas heat exchange unit 26 is in thermally conductive contact with the connection between the C 9 converter and the mixing chamber 21 and is adapted to extract the excess heat from the connection and thus extract the excess heat contained in the hot synthesis gas. The extracted heat can be used, for example, to preheat the water that is introduced into the C 9 converter. For this heat transfer a so-called counterflow heat exchange unit as known in the prior art would be particularly appropriate.
    [0064] The H2 27 heat exchange unit is in thermally conductive contact with the connection between the hydrocarbon converter 3 and the mixing chamber 21 and is adapted to extract the excess heat from the connection and thus from that contained in the hot hydrogen. The heat extracted in one of the heat exchange units 25, 26 or 27 can be used to heat other areas of the plant, and specifically to keep the C converter warm or to preheat the water that is introduced in the C converter. A portion of the heat can be converted into electricity, for example, by a steam generator and a steam turbine or by another suitable device.
    [0065] The operation of plant 20 to generate synthesis gas is, in relation to the operation of hydrocarbon converter 3 and the C 9 converter, similar to the operation described above of plant 1 according to Fig. 1. In plant 20 for to generate synthesis gas, a desired ratio of the hydrogen to CO mixture is defined in the mixing chamber and is diverted through the synthesis gas outlet 24 of the mixing chamber 21, depending on the desired composition of the synthesis gas. Preferably, but not necessarily, hydrogen is, as described, supplied by hydrocarbon converter 3. Other sources of hydrogen can be considered, particularly a second hydrocarbon converter 3, particularly a low temperature hydrocarbon converter. If not all available quantity of synthesis gas and / or all available quantity of H2 are used, those parts of the gases, for example, synthesis gas and / or H2, which are not mixed in the mixing chamber can be processed separately.
    [0066] Fig. 3 shows a plant 30 for the generation of synthetic functionalized and / or non-functionalized hydrocarbons comprising a plant 10 for the generation of water gas (as shown in Fig. 1) and a CO 31 converter. Those parts of the plant corresponding to plant 1 are not explained in detail in order to avoid repetition. The CO converter 31 is located downstream from the C converter 9 and comprises a synthesis gas inlet 32 to introduce synthesis gas, an H2 input 33 to introduce hydrogen and a hydrocarbon outlet 34 to discharge functionalized synthetic hydrocarbons and / or non-functionalized. The synthesis gas inlet 32 of the CO 31 converter is connected to the synthesis gas outlet 12 of the C 9 converter through the synthesis gas connection 35. The H2 input 33 of the CO 31 converter is connected to the H2 outlet. 6 of the hydrocarbon converter 3 through the H2 connection 36.
    [0067] It should be noted that the H2 33 input of the CO 31 converter and the H2 36 connection are optional elements. Depending on the composition of the synthesis gas, which leaves the C 9 converter and depending on the functionalized and / or non-functionalized synthetic hydrocarbons to be generated in the CO 31 converter, the synthesis gas already has the right composition for further processing by the converter of CO 31 at the moment when the synthesis gas leaves the synthesis gas outlet 12 of the C 9 converter. In this case, it is not necessary to introduce hydrogen via the H2 36 connection. Optionally, the H2 36 connection can also serve to introduce another material, for example, CO to reduce the H2 content of the synthesis gas or an alkene for the synthesis of an aldehyde (hydroformylation).
    [0068] Plant 30 for optionally generating hydrocarbons also comprises heat exchange units 25, 26, 27 described together with plant 20 (Fig. 2), which is the C 25 heat exchanger, the heat exchanger of synthetic gas 26 and the H2 heat exchanger 27, all operating in the manner described above (see description in Fig. 2).
    [0069] The CO 31 converter can be any CO converter to generate functionalized and / or non-functionalized synthetic hydrocarbons. In the embodiment shown in Fig. 3, the CO converter is preferably a Fischer-Tropsch converter, a Bergius-Pier converter or a Pier converter with a suitable catalyst and a control unit for temperature and / or pressure.
    [0070] In one embodiment, the CO 31 converter comprises a Fischer-Tropsch converter. A Fischer-Tropsch converter catalytically transforms a synthesis gas into hydrocarbons and water. Various types of Fischer-Tropsch reactors and Fischer-Tropsch processes are known to the person skilled in the art and are not explained in detail. The main reaction equations are as follows: n CO + (2n + 1) H2 -> • Cn H2n + 2 + n H2O for alkanes n CO + 2n H2 - »Cn H2n + n H2O for alkenes n CO + 2n H2 - ► Cn H2n + 1OH + (n - 1) H2O for alcohols
    [0071] Fischer-Tropsch processes can be performed as high temperature processes or as low temperature processes, where the process temperatures are usually in the range of 200 to 400 ° C. Known variants of the Fischer-Tropsch process are, among others, the Hochlast synthesis, the Synthol synthesis and the Shell SMDS process (SMDS = Shell Middle Distillate Synthesis). A Fischer-Tropsch converter typically produces a moist gas hydrocarbon compound (propane, butane), gasoline, kerosene, soft paraffin, hard paraffin, methane, diesel fuel or a mixture of several of these. It is known by a person skilled in the art that the Fischer-Tropsch synthesis is exothermic. The reaction heat from the Fischer-Tropsch process can be used, for example, by means of a heat exchange unit (not shown in the figures) to preheat the water. For example, a two-stage preheating process for water to be introduced in the C 9 converter is considered, in which a first preheating step carried out with the excess heat from the CO 31 converter (in the form of a Fischer-Tropsch converter) and subsequently the additional water heating step by means of the heat from one or more of the heat exchange units 25, 26, 27.
    [0072] In an alternative embodiment, the CO 31 converter comprises a Bergius-Pier converter or a combination of a Pier converter with a MtL converter (MtL = Methanol-to-Liquid).
    [0073] In a Bergius-Pier converter, the Bergius-Pier process, which is well known to a person skilled in the art, is carried out, in which hydrocarbons are generated by hydrogenation of carbon with hydrogen in an exothermic chemical reaction. The product range of the Bergius-Pier process depends on the reaction conditions and the control of the reaction process. Mainly liquid products are obtained, which can be used as fuels, for example, heavy and medium oils. The known variants of the Bergius-Pier process are, for example, the Konsol process and the H-Coal process.
    [0074] In the aforementioned combination of a Pier converter with a MtL converter, the synthesis gas is initially transformed into methanol according to the Pier process. The MtL converter is a converter that converts methanol into gasoline. A widespread process is the ExxonMobil EsL process, respectively Esso. The raw material of the MtL converter is typically methanol, for example, from the Pier converter. The output product generated by the MtL converter is typically gasoline, which is suitable for operating an Otto engine.
    [0075] In summary, it can be said that the CO 31 converter, regardless of the operating principles explained above, generates synthetic hydrocarbons functionalized and / or non-functionalized from CO and H2 as its final or output products. By means of a heat exchange unit, the process heat produced during the exothermic transformation in the CO 31 converter, can be used to heat different sections of the plant or to generate electricity in order to increase the efficiency of the described plant.
    [0076] As a hydrocarbon mixture, which cannot yet be processed directly or profitably sold as a final product after separation and specification, is obtained as output products from the CO 31 converter, these hydrocarbons, for example, methane or short-chain alkanes, can be recycled in the process described above. For this purpose, the plant 30 comprises a recycle connection 39, which can direct a portion of the synthetically generated hydrocarbons back to the hydrocarbon inlet 4 of the hydrocarbon converter 3. Depending on the composition of the recycled, synthetically generated hydrocarbons, one step of treatment or separation of unsuitable hydrocarbons is carried out before the introduction of unsuitable hydrocarbons into the hydrocarbon inlet 4.
    [0077] Fig. 4 shows an additional modality of a plant 40 to generate functionalized and / or non-functionalized synthetic hydrocarbons. The plant 40 comprises the plant 20 described above to generate a synthesis gas as well as a CO 31 converter as described above with reference to the embodiment in Fig. 3. The synthesis gas outlet 24 of the mixing chamber 21 is connected to the inlet synthesis gas 32 from the CO 31 converter. The mixing chamber 21 is defined in such a way that it provides a synthesis gas adapted to the needs of the CO 31 converter in use at the synthesis gas outlet 24. The other elements of the plant 40 are the same as described above and the operation of the individual elements occurs essentially in the manner described above.
    [0078] It is considered that, depending on the size of the plant, a plurality of hydrocarbon converters are operated in parallel in order to provide the desired transformation capacity. As mentioned above, the hydrocarbon converters can be constructed as high temperature hydrocarbon converters and / or as low temperature hydrocarbon converters. A high temperature hydrocarbon converter operates at temperatures above 1000 ° C and a low temperature hydrocarbon converter operates at temperatures between 200 and 1000 ° C, where an additional energy source, for example, a microwave unit , can be provided to directly insert energy into the hydrocarbon to achieve decomposition of the hydrocarbon to carbon and hydrogen.
    [0079] As an example for a plant with a plurality of hydrocarbon converters operated in parallel, Fig. 5 shows an additional modality of plant 30 for generating functionalized and / or non-functionalized synthetic hydrocarbons. Fig. 5 uses the same reference numbers as in the previous modalities, as the same or similar elements are described. In the modality shown in Fiq. 5, a combination of a high temperature hydrocarbon converter 3a and a low temperature hydrocarbon converter 3b is shown instead of a single hydrocarbon converter 3.
    [0080] The high temperature hydrocarbon converter 3a comprises a hydrocarbon inlet 4a, a first outlet 5a for discharging carbon and a second outlet 6a for discharging hydrogen. Again, a single outlet 5a can be provided for a mixture (particularly an aerosol) of carbon and hydrogen. The first output 5a is connected to the C 11 input of the C 9 converter through a connection 8. The optional second output 6a of the high temperature hydrocarbon converter 3a is connected to the H2 33 input of the CO 31 converter. high temperature hydrocarbon 3a can optionally further comprise a carbon outlet (not shown in Fig. 5).
    [0081] The low temperature hydrocarbon converter 3b comprises the process chamber having a hydrocarbon inlet 4b, the first outlet 5b for discharging carbon, a second outlet 6b for discharging hydrogen and an optional third outlet 7b for discharging carbon. Preferably, the low temperature hydrocarbon converter 3b comprises a separation unit for separating hydrogen and carbon after decomposition and for directing hydrogen and carbon to their respective outlets. The first output 5b is optionally connected to the C 11 input of the C 9 converter via connection 8, but it can also be connected to the carbon collection unit. The second output 6b of the low temperature hydrocarbon converter 3b is connected to the H2 input 33 of the CO 31 converter. The optional third output 7b is connected to the carbon collection unit, from which the collected carbon can be removed, for example , such as carbon black, activated carbon or in another form.
    [0082] As noted above, the H2 33 input from the CO 31 converter and the H2 36a, 36b connections are optional elements, if the introduction of hydrogen via the H2 36a, 36b connections is not necessary.
    [0083] The hydrocarbon introduced into hydrocarbon inlet 4a and the hydrocarbon introduced into hydrocarbon inlet 4b can be the same hydrocarbon or can be different hydrocarbons. A hydrocarbon from a first hydrocarbon source can be introduced into hydrocarbon inlet 4a, for example, natural gas from a natural gas source. However, for example, synthetically generated functionalized and / or non-functionalized hydrocarbons can be introduced into hydrocarbon inlet 4b of the low temperature hydrocarbon converter 3b, for example, via the aforementioned, optional recycle connection 39. Because of the use of several hydrocarbon converters operated in parallel 3, 3a, 3b, the plant 30 can be dimensioned easier, it can be controlled easier and different types of carbon can be produced.
    [0084] Furthermore, the high temperature hydrocarbon converter 3a can, for example, be advantageously used to generate "hot" carbon, preferably at a temperature above 1000 ° C, for the process transformation in the C 9 converter. In particular, the high temperature hydrocarbon converter 3a can operate in this case without a separation unit, since the C-H2 mixture, obtained by decomposition, can be introduced directly into the C converter. In this case, the C converter 9 produces a synthesis gas having a C-H2 mixing ratio of, for example, about 1: 1 at the outlet.
    [0085] The low temperature hydrocarbon converter 3b, however, is primarily used to provide additional hydrogen for the generation of a synthesis gas or a C-H2 mixture having a C-H2 mixing ratio greater than 1: 3 in the CO 31 converter. Since no heat transfer from the low temperature hydrocarbon converter 3b to a subsequent process is required, the low temperature hydrocarbon converter 3b can advantageously be operated at temperatures below 1000 ° C and preferably the temperature lowest possible.
    In this way, a portion of the carbon produced in the hydrocarbon converters 3a, 3b (preferably the portion of the high temperature hydrocarbon converter 3a) can be introduced into the C 9 converter during operation of plant 30, while a another portion (preferably the low temperature hydrocarbon converter portion 3b) can be diverted from the process as a raw material to produce more products. Such products are, for example, carbon black or industrial soot, activated carbon, special types of carbon such as carbon disks and carbon cones etc., which is obtained as a solid black powder. This carbon is an important technical product, which can, for example, be used as a filler in the rubber industry, such as pigment soot for printing colors, printing inks, inks or as a raw material for the production of electrical components, for example , zinc-carbon batteries, and for the production of cathodes or anodes. Any excess hydrogen can be diverted to the chemical industry or can be used to generate electricity (by burning or by means of a fuel cell), in which the low temperature hydrocarbon converter 3b is preferably operated in such a way that it only provides the additional hydrogen needed.
    [0087] Fig. 6 shows an alternative modality of the plant described above 40 for generating functionalized and / or non-functionalized synthetic hydrocarbons, so that a plurality of high temperature parallel operated and / or low temperature hydrocarbon converters are provided as well. The plant 40 for generating hydrocarbons shown in Fig. 6 differs from the plant 30 shown in Fig. 5 in such a way that the mixing chamber 21 is located upstream of the CO converter 31. The mixing chamber 21 mixes a synthesis gas specifically adapted for the CO 31 converter and delivers the synthesis gas to the CO 31 converter. The elements shown in Fig. 6 have already been described above and work according to the principles described above. Therefore, no detailed description is given in order to avoid repetition.
    [0088] Figs. 7 and 8 show modalities of plants 20 and 30 comprising a C 25 heat exchange unit, a synthesis gas heat exchange unit 26 and an H2 heat exchange unit 27, each of which is connected to a motor / generator device 45. The motor / generator device 45 is suitable for at least partially generating electricity from excess heat from different sections of the plant, wherein said electricity can either be fed into the main grid or can be used to operate plant 20, especially the hydrocarbon converter (s). In addition, the engine / generator device 45 can be connected to a heat exchange unit (not shown in Fig. 8), which dissipates the heat generated by the exothermic transformation process occurring inside the CO 31 converter. on the one hand the CO converter can be cooled in a controlled and regulated mode, which is advantageous for the operation of the process, and on the other hand electricity can be generated. The engine / generator device 45 can be any device that is suitable for transforming thermal energy into electricity, for example, a combination of a steam turbine and a generator or a piston engine and generator.
    [0089] During operation, the engine / generator device 45 turns the excess heat from the plant into electricity, that is, the heat that is not necessary for water-carbon transformation.
    [0090] The engine / generator device 45 and the heat exchange units 25, 26 and 27 are optional elements that can be used in all the plants described above. Due to the operating temperature in the respective hydrocarbon converter 3, 3a, 3b, the carbon diverted from the respective second carbon outlets 7, 7a, 7b also contains significant amounts of thermal energy. Depending on the desired temperature of the bypassed carbon, a large amount of this thermal energy can be dissipated by means of heat exchange units not shown in the figures, and the heat can be reused in the processes described in this document and / or can be transformed into electricity. using the engine / generator device 45.
    [0091] In plants 30 and 40 to generate functionalized and / or non-functionalized synthetic hydrocarbons, cooling of hydrogen from hydrocarbon converters 3, 3a, 3b and / or cooling of the synthesis gas from the C 9 converter is carried out only as long as the temperature of the hydrocarbons and hydrogen does not fall below the operating temperature of the CO 31 converter. The operating temperature of the CO 31 converter is usually between 200 and 400 ° C, depending on the chosen process.
    [0092] In all the plants described above, hydrocarbon converter 3 can be a high temperature reactor operating at a temperature of more than 1000 ° C (for example, a high temperature Kvaerner reactor) or a low temperature reactor operating at a temperature between 200 ° C and 1000 ° C (for example, a low temperature Kvaerner reactor). A recently tested low temperature reactor operates at temperatures between 400 and 900 ° C. In the case of a low temperature reactor operating at temperatures between 200 and 900 ° C, the carbon introduced is considered to be preheated at connection 8 between the hydrocarbon converter 3 and the C 9 converter, such as the C 9 converter operates at temperatures between 800 and 1700 ° C and preferably 1000 to 1200 ° C. In addition, it becomes clear from Figs. 7 and 8 that a combination of high temperature and / or low temperature converters can be used in all plants 1, 20, 30 and 40 described above.
    [0093] In all plants 1, 20, 30 and 40 described above, a portion of the carbon generated in hydrocarbon converters 3, 3a, 3b can be diverted as carbon black, as activated carbon or as another raw material since that said carbon is not converted into the C 9 converter of plant 1, 20, 30, 40. It should also be noted that, in all the plants described above, a plurality of C converters can be provided, in which each of these C converters can turn a portion of the carbon into syngas when water is added. In addition, optionally the recycling of unwanted functionalized and / or non-functionalized synthetic hydrocarbons produced in the CO 31 converter by feeding unwanted hydrocarbons into hydrocarbon intakes 4, 4a, 4b of the hydrocarbon converter 3 can be performed in all plants 30 and 40 described above.
    [0094] In plants 1, 20, 30, 40 and in the methods to generate synthesis gas and / or functionalized and / or non-functionalized synthetic hydrocarbons, excess hydrogen can be produced. Excess hydrogen is left, for example, with a synthesis gas having a low H2 content, and, depending on the synthetic hydrocarbons generated in the CO 31 converter, introducing hydrogen into the mixing chamber 21 or into the CO 31 converter may not be necessary. In these cases, the excess or excess of hydrogen can be transformed into electricity either directly by burning or by means of a fuel cell. In this way, the method operates substantially without the entry of external electricity. This is particularly advantageous with plants that are operated in remote locations, where a powerful general grid is not available. It should also be noted that a portion of the hydrogen produced in the hydrocarbon converter 3, can be extracted directly from the process and traded as a commodity.
    [0095] In all plants, the flows of carbon, synthesis gas and hydrogen and external CO, respectively, between converters 3, 9, 31 and mixing chamber 21 can be controlled by means of valves, shutters, cursors etc. . In particular, it is considered that the influx of synthesis gas and hydrogen respectively CO into the CO 31 converter can be controlled by valves. Then, mixing of synthesis gas and hydrogen respectively CO in the desired ratio takes place directly in the CO 31 converter.
    [0096] In all the plants described above, the CO 31 converter can consist of a plurality of CO converters (not shown in the figures), in which the total amounts of hydrogen generated and separated in the hydrocarbon converters 3, 3a, 3b and the synthesis gas generated in the CO 9 converter, can be arbitrarily divided between the plurality of the CO converters. The individual CO converter has one of the designs and operating mode described above. CO converters can have the same design or different designs or modes of operation. In a modality having different CO converters, the individual CO converters can each be operated with differently formed synthetic gas and produce different final products.
    [0097] To further illustrate the methods, some examples follow:
    [0098] Example 1
    [0099] If 1 part of methane is decomposed in the hydrocarbon converter, then a part of carbon and two parts of hydrogen will be obtained. The carbon reacts with a part of water in the C converter and forms a part of carbon monoxide and a part of hydrogen. After adding 1.1 parts of hydrogen, the syngas can be reacted to paraffin in the CO converter. After that, enough hydrogen is still available to crack diesel paraffin, Otto fuel or kerosene in an additional step.
    [0100] Example 2
    [0101] If 1 part of propane (butane) is decomposed in the hydrocarbon converter, then 3 (4) parts of carbon and 4 (5) parts of hydrogen will be obtained. The carbon reacts with 3 (4) parts of water in the C converter and forms 3 (4) parts of carbon monoxide and 3 (4) parts of hydrogen. After adding 3.3 (4.4) parts of hydrogen, the synthesis gas can be reacted to paraffin in the CO converter. In both cases, the amount of residual hydrogen is just enough to crack Diesel paraffin, Otto fuel or kerosene in an additional step.
    [0102] Example 3
    [0103] If 1 part of heavy oil (for example, C20H42) is decomposed in the hydrocarbon converter, then 20 parts of carbon and 21 parts of hydrogen will be obtained. The carbon reacts with 20 parts of water in the C converter and forms 20 parts of carbon monoxide and 20 parts of hydrogen. After adding 21 parts of hydrogen, the syngas can be reacted to 20 parts of methanol in a converter other than CO.
    [0104] Since, in the methods described in this document, the hydrogen generated by the hydrocarbon decomposition in hydrocarbon converter 3 is separated from the carbon also formed in the decomposition step, the separated hydrogen can be added at any desired rate to a gas synthesis having low hydrogen content after forming said synthesis gas having low hydrogen content. In this way, a range of hydrogen to CO ratios between 1.0 and 3.0 can be achieved. By partially oxidizing the excess carbon, a ratio <1.0 can be obtained, and by not using the excess carbon, a ratio> 3.0 can be obtained. The invention has explained in some detail with respect to the preferred embodiments, in which the individual characteristics of the described embodiments can be freely combined with each other as they are compatible. In addition, the individual characteristics of the described modalities can be omitted as these characteristics are not absolutely necessary. Many modifications and deviations will be obvious to a person skilled in the art without departing from the scope of the invention. In a particularly simple plant modality for generating functionalized and / or non-functionalized synthetic hydrocarbons, the C converter can be designed, for example, as a simple pipe (for example, as a pipe from an outlet of a high temperature hydrocarbon converter) without separation unit), in which the incoming water leads to said tube. The water inlet must join the said tube so that the two steam media are well mixed. The tube must be insulated and could be connected to a heating unit, for example, in an inlet section in order to heat the tube, especially at the beginning of the operation to an operating temperature. Further downstream, the tube could be connected to a heat exchanger adapted to extract the excess heat and use this heat to heat other sectors of the plant and / or to generate electricity. In addition, the tube may comprise a hydrogen inlet tube (for example, downstream of the heat exchanger) so that the same tube not only functions as a C converter, but also functions as a mixing chamber to generate a gas of synthesis having a particular mixing ratio. The hydrogen inlet tube can originate, for example, from a hydrogen outlet from a low temperature hydrocarbon converter (having a separation unit). In this case, an end of the pipe outlet, where a synthesis gas having a predetermined mixing ratio can be discharged, could end up in a CO converter.
    权利要求:
    Claims (21)
    [0001]
    1. METHOD FOR GENERATING SYNTHESIS GAS, characterized by comprising the following steps: decomposing a fluid containing hydrocarbon into carbon and hydrogen by introducing energy, the energy being at least partially provided by heating, in which the decomposition step occurs at a temperature above 1000 ° C; and where carbon and hydrogen have a temperature of at least 200 ° C after the decomposition step; put the water in contact with at least a portion of the carbon generated by the decomposition step at a temperature between 800 and 1700 ° C, in which by placing the carbon in contact with the water, the carbon obtained by the decomposition step cooled by no more than 50% in ° C with respect to its temperature after the decomposition step; transform at least a portion of the water and the carbon obtained by the decomposition step into syngas; wherein the carbon obtained by the decomposition step and the hydrogen obtained by the decomposition step are brought into contact with water together.
    [0002]
    2. METHOD FOR GENERATING SYNTHESIS GAS, characterized by comprising the following steps: decomposing a fluid containing hydrocarbon into carbon and hydrogen through the introduction of energy, the energy being at least partially provided by heating, where the decomposition step occurs at a temperature above 1000 ° C; and where carbon and hydrogen have a temperature of at least 200 ° C after the decomposition step; put the water in contact with at least a portion of the carbon generated by the decomposition step at a temperature between 800 and 1700 ° C, in which by placing the carbon in contact with the water, the carbon obtained by the decomposition step cooled by no more than 50% in ° C with respect to its temperature after the decomposition step; transform at least a portion of the water and the carbon obtained by the decomposition step into synthesis gas; in which the carbon obtained by the decomposition step is at least partially separated from the hydrogen obtained by the decomposition step before the step of bringing the carbon into contact with water, and in which at least a portion of the separated hydrogen is added to the gas synthesis generated by the transformation.
    [0003]
    METHOD according to either of claims 1 or 2, characterized in that the carbon is brought into contact with water at a temperature of at least 1000 ° C, particularly at a temperature between 1000 ° C and 1200 ° C.
    [0004]
    METHOD according to any one of the preceding claims, characterized in that the heating required to reach the temperature between 800 and 1700 ° C for the transformation originates essentially entirely from the heating that is provided to decompose the hydrocarbon-containing fluid.
    [0005]
    5. METHOD according to any one of the preceding claims, characterized by at least a portion of the heating of at least a portion of the carbon obtained by the decomposition step and / or a portion of the hydrogen obtained by the decomposition step and / or a portion of the synthesis gas to be used to heat the water before putting the water in contact with the carbon and / or to be used to heat the process chamber, in which the water is brought into contact with the carbon and / or is used to generate electricity, in which electricity particularly can be provided as an energy carrier to introduce energy to decompose the hydrocarbon-containing fluid.
    [0006]
    6. METHOD according to any one of the preceding claims, characterized in that the energy to decompose the hydrocarbon-containing fluid is primarily introduced by means of a plasma, and in which the decomposition step is preferably carried out in a Kvaerner reactor.
    [0007]
    7. METHOD, according to claim 6, characterized by the carbon generated by the decomposition and the hydrogen generated by the decomposition being placed in contact with the water in the form of an aerosol.
    [0008]
    8. METHOD according to claim 2, characterized in that at least one of the additional hydrogen or additional carbon monoxide is added to the synthesis gas, and in which at least a portion of the additional hydrogen is generated by the decomposition of a fluid containing hydrocarbon at a temperature below 1000 ° C, particularly below 600 ° C, by means of a microwave plasma.
    [0009]
    9. METHOD FOR GENERATING SYNTHETIC HYDROCARBONS, FUNCTIONED AND / OR NOT FUNCTIONED, characterized in that first a synthesis gas is generated, as defined in the method of any one of claims 1 to 8, and in which the synthesis gas is placed in contact with a suitable catalyst in order to cause the transformation of the synthesis gas into functionalized and / or non-functionalized synthetic hydrocarbons, where the temperature of the catalyst and / or the synthesis gas is controlled by an open circuit or regulated by a closed circuit for a pre- temperature.
    [0010]
    10. METHOD, according to claim 9, characterized by the transformation of the synthesis gas to be carried out by means of one of the following: a Fischer-Tropsch process, an SMDS process, a Bergius-Pier process, a Pier process or a combination of a Pier process and a MtL process.
    [0011]
    11. METHOD according to any one of the preceding claims, characterized in that the hydrocarbon-containing fluid to be decomposed is natural gas, methane, wet gases, heavy oil or a mixture of these.
    [0012]
    12. EQUIPMENT FOR GENERATING SYNTHESIS GAS, characterized by comprising: a hydrocarbon converter to decompose a fluid containing hydrocarbon into carbon and hydrogen, in which the hydrocarbon converter comprises at least one process chamber having at least one inlet for a fluid containing hydrocarbon and at least one outlet for carbon and / or hydrogen and at least one unit to introduce energy into the process chamber, which is constructed in such a way that it is capable of at least locally generating temperatures above 1000 ° C, the energy consisting of less partially from heat; a C converter for the transformation of water and carbon, the C converter comprising at least one additional process chamber having at least one inlet for water, at least one inlet for at least carbon and at least one outlet, wherein the inlet for at least the carbon is directly connected to at least one outlet of the hydrocarbon converter; wherein the hydrocarbon converter, at least one outlet of the hydrocarbon converter, the C converter and at least one input of the C converter are adapted to simultaneously direct said carbon and said hydrogen produced in the hydrocarbon converter inwards of the C converter.
    [0013]
    13. EQUIPMENT FOR GENERATING SYNTHESIS GAS, characterized by comprising: a hydrocarbon converter to decompose a fluid containing hydrocarbon into carbon and hydrogen, in which the hydrocarbon converter comprises at least one process chamber having at least one inlet for a fluid containing hydrocarbon and at least one outlet for carbon and / or hydrogen and at least one unit to introduce energy into the process chamber, which is constructed in such a way that it is capable of at least locally generating temperatures above 1000 ° C, the energy consisting of less partially from heat; a C converter for the transformation of water and carbon, the C converter comprising at least one additional process chamber having at least one inlet for water, at least one inlet for at least carbon and at least one outlet, wherein the inlet for at least the carbon is directly connected to at least one outlet of the hydrocarbon converter; wherein a separation unit is provided to separate the carbon obtained by the decomposition and the hydrogen obtained by the decomposition, the separation unit having separate outlets for the separate materials coming from the separation unit, where the outlet for the carbon is connected to the converter of C, in which a separate inlet tube for hydrogen from the separation unit is provided, the inlet tube for hydrogen leading into the C converter or into a mixing chamber located downstream.
    [0014]
    Apparatus according to any one of claims 12 to 13, characterized in that at least one unit for introducing energy into the process chamber comprises a plasma unit, particularly a microwave plasma unit.
    [0015]
    Apparatus according to one of claims 12 to 14, characterized in that the process chamber of the C converter is formed by an outlet tube of the hydrocarbon converter, in which the outlet tube is connected to an inlet for water.
    [0016]
    16. Apparatus according to one of claims 12 to 15, characterized in that the hydrocarbon converter comprises a Kvaerner reactor.
    [0017]
    17. Apparatus according to claim 14 or 16, characterized in that the hydrocarbon converter is further adapted to produce an aerosol comprising carbon and hydrogen.
    [0018]
    Apparatus according to one of claims 12 to 17, characterized in that it has at least one additional hydrocarbon converter to decompose a fluid containing hydrocarbon into carbon and hydrogen, the additional hydrocarbon converter comprising: at least one process chamber having at least at least one inlet for the hydrocarbon-containing fluid; at least one unit for introducing energy into the process chamber of the additional hydrocarbon converter, the energy at least partially consisting of heat; a separation unit to separate the carbon obtained by the decomposition and the hydrogen obtained by the decomposition, with the separation unit having separate outlets for carbon and hydrogen, where the outlet for hydrogen is connected to the separate inlet tube for hydrogen.
    [0019]
    19. Apparatus according to claim 18, characterized in that at least one additional hydrocarbon converter is of a type performing decomposition at temperatures below 1000 ° C, particularly below 600 ° C by means of a microwave plasma.
    [0020]
    20. APPLIANCE FOR TRANSFORMING SYNTHESIS GAS INTO SYNTHETIC HYDROCARBONS FUNCTIONED AND / OR NOT FUNCTIONED, characterized by comprising: an apparatus, as described in any of claims 12 to 19; and a CO converter having a process chamber, in which a catalyst is located, and means for bringing the synthesis gas into contact with the catalyst, and a control unit for the control of the open circuit or the regulation of the closed circuit a temperature of the catalyst and / or the synthesis gas to a predetermined temperature.
    [0021]
    21. APPARATUS according to claim 20, characterized in that the CO converter comprises one of the following: a Fischer-Tropsch converter, an SMDS converter, a Bergius-Pier converter, a Pier converter or a combination of a Pier converter with a converter MtL.
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    同族专利:
    公开号 | 公开日
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-08-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102011122562|2011-12-20|
    DE102011122562.9|2011-12-20|
    DE102012008933.3|2012-05-04|
    DE102012008933|2012-05-04|
    DE102012010542A|DE102012010542A1|2011-12-20|2012-05-29|METHOD AND APPARATUS FOR GENERATING SYNTHESEGAS|
    DE102012010542.8|2012-05-29|
    PCT/EP2012/005310|WO2013091879A1|2011-12-20|2012-12-20|Process and system for generating synthesis gas|
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