CN117242211A - Method and apparatus for producing hydrocarbons - Google Patents
Method and apparatus for producing hydrocarbons Download PDFInfo
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- CN117242211A CN117242211A CN202280031224.1A CN202280031224A CN117242211A CN 117242211 A CN117242211 A CN 117242211A CN 202280031224 A CN202280031224 A CN 202280031224A CN 117242211 A CN117242211 A CN 117242211A
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 159
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 149
- 238000000034 method Methods 0.000 title claims abstract description 88
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 135
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000007789 gas Substances 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910001868 water Inorganic materials 0.000 claims abstract description 74
- 239000001257 hydrogen Substances 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 41
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 16
- 238000011084 recovery Methods 0.000 claims abstract description 15
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- -1 C 3 Hydrocarbons Chemical class 0.000 claims description 26
- 239000002028 Biomass Substances 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002485 combustion reaction Methods 0.000 claims description 9
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 7
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 239000000758 substrate Substances 0.000 abstract description 19
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 239000002912 waste gas Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 25
- 239000013505 freshwater Substances 0.000 description 12
- 238000002309 gasification Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000003502 gasoline Substances 0.000 description 7
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 150000002835 noble gases Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing hydrocarbons (6), comprising the following steps: a) Performing electrolysis (3) of water, thereby generating hydrogen and oxygen; b) Producing a carbon source having or consisting essentially of carbon dioxide and/or carbon monoxide; c) Producing (5) hydrocarbons (6) from the hydrogen produced in step a) and the carbon source produced in step b), wherein at least part of the produced hydrocarbons are present as liquid hydrocarbons and waste gases with hydrogen, carbon dioxide and/or carbon monoxide are formed in addition to the hydrocarbons (6); d) Separating the off-gas from the liquid hydrocarbon (6); e) An exhaust gas recovery (8) is performed in which the reaction of the exhaust gas with the oxygen and/or with water produced in step a) is performed, thereby forming a recovered product with carbon dioxide and/or carbon monoxide, water and optionally hydrogen. The process may be particularly advantageous for the production of hydrocarbons using methanol as a preferred product from methanol synthesis 13. The methanol in turn can be further used as an initial material (substrate) or intermediate for the production (19) of further high value liquid hydrocarbons.
Description
Technical Field
The present invention relates to a method and apparatus for producing hydrocarbons.
Background
Regenerated hydrocarbons are characterized in that they are produced by using a regeneration substrate. The regeneration substrate may be, for example, regenerated carbon dioxide (which is obtained, for example, from biomass) and regenerated hydrogen (which is obtained, for example, by electrolysis of water, in particular by using regeneratively generated electricity). The production of the regeneration substrate and the conversion of the regeneration substrate into regenerated hydrocarbons is energy intensive and thus also cost intensive. The cost of currently used for producing regenerated hydrocarbons is several times the production cost of producing the same hydrocarbons from fossil feedstocks.
Different routes currently exist to achieve the production of regenerated hydrocarbons. In this regard, the most important routes will only be briefly summarized, which are the Fischer-Tropsch synthesis (Fischer-Tropsch), the Alcohol-to-Fuel-Route (Alcohol-to-Fuel-Route), the Methanol-Route (Methanol-Route) and the TIGAS process (TIGAS-Verfahren).
Fischer-Tropsch synthesis allows the production of different synthetic hydrocarbon fuels, in particular diesel, kerosene, petrol and liquefied gases. However, this technique has two disadvantages: the first disadvantage is that the products are produced together and the selectivity is small, so that all the products must be marketed at the same time. By this route, the desired production of a particular product with only small amounts of other products being produced at the same time cannot be achieved in practice. A second disadvantage of fischer-tropsch synthesis is that carbon monoxide is required as a substrate. Accordingly, the regeneratively obtained carbon dioxide must first be reduced to carbon monoxide, which is only possible with two immature technologies, reverse-Water-Gas-Shift (RWGS) and Solid-Oxide-Electrolysis (SOEC). The high temperatures in the range of over 800 ℃ associated with RWGS and SOEC place extreme demands on the required materials and catalysts. Furthermore, under these conditions, coking of the active surface may be relatively rapid.
The alcohol-to-fuel route is based on the production of ethanol by syngas fermentation, in which carbon dioxide and/or carbon monoxide and hydrogen are converted to ethanol by microbiological means. The ethanol is then dehydrated to ethylene, which is oligomerized to oligomers. The oligomers are then hydrogenated to give hydrocarbons. In this way, different hydrocarbons, such as kerosene, can be produced with relatively high selectivity. In addition to the typically low space-time yields of syngas fermentation, different aspects of scale-up are seen as critical. The problem thus arises as to whether the alcohol fuel route will dominate in the future on a large industrial scale.
Based on the use of carbon dioxide and hydrogenAnd/or from carbon monoxide and hydrogenThe methanol route to methanol and further processing of methanol to hydrocarbons is more selective than fischer-tropsch synthesis but less selective than the alcohol to fuel route. The possibility of scale-up is positively evaluated and the direct use of regenerated carbon dioxide is another significant advantage of this route. A disadvantage of the prior art is the need to separate the reaction water formed in methanol synthesis with carbon dioxide by energy intensive distillation. Methanol dehydrated in this way can then be converted into a different end product. Methanol to kerosene technology is still in the development stage (pilot scale). Methanol to olefins technology aimed at producing ethylene, propylene and butenes has been developed in part on a production scale. Most notable is the methanol to gasoline technology, which has been used to produce synthetic gasoline on a large scale. In addition to the main product gasoline, liquefied gas and small amounts of C are formed 1 /C 2 A hydrocarbon mixture.
Fig. 1 shows a method according to the methanol route according to the prior art. A mass flow 78 comprising or consisting of carbon dioxide and/or carbon monoxide and hydrogen is fed to the synthesis 13 of methanol. Thereby producing a mass stream 71 comprising methanol, water and unconverted substrate. Even for very high conversions of more than 90%, this loss is not acceptable. Separation 14 of mass flow 71 is thus carried out, wherein in separation 14 water and methanol are separated from unconverted substrate by condensation. Unconverted substrate forms a mass flow 72 which is again fed to the synthesis 13 of methanol. The mixture of methanol and water formed in the separation 14 is fed in mass flow 73 to the distillation 15 in order to separate the methanol from the water. The water may be delivered to the wastewater treatment 17 in a mass flow 75. Since the subsequent hydrocarbon synthesis 19 is carried out in the gas phase, methanol must be fed to the condensate 16 (condenser at the top of the distillation column) in a mass flow 74 and to the vaporisation 18 in a subsequent mass flow 76. A portion of condensate 16 formed in condensate 16 may be returned to the top of the column as mass flow 79. A first cooling 81 in the separation 14, a first heating 82 in the distillation 15, a second cooling 83 in the condensation 16, and a second heating 84 in the evaporation 18. This makes the process energy-intensive and thus cost-intensive. Nevertheless, it is also necessary to return unconverted substrates to the mass flow 72, as will be appreciated in view of the high energy consumption in regeneratively capturing these substrates.
An alternative to methanol to gasoline technology is the TIGAS process, which produces a mixture primarily containing methanol, dimethyl ether and water in the first step. The mixture is directly converted to gasoline without separating water. Despite this simplification and the different technical and economic advantages, TIGAS technology is currently not suitable for the production of regenerated hydrocarbons, since, like fischer-tropsch synthesis, the TIGAS process uses carbon monoxide as substrate (3co+3h 2 →CH 3 -O-CH 3 +CO 2 ) The problems of the immature RWGS technology and SOEC technology also occur here.
In order to be able to produce liquid hydrocarbons in a cost-effective manner, it is necessary to use the substrates introduced as completely as possible in all processes and/or to use as little energy as possible in the processes.
Disclosure of Invention
It is therefore an object of the present invention to provide a method and apparatus which can produce liquid hydrocarbons at low cost.
The method for producing hydrocarbons according to the invention comprises the steps of: a) Performing electrolysis of water, thereby generating hydrogen and oxygen; b) Producing a carbon source having or consisting essentially of carbon dioxide and carbon monoxide; c) Producing hydrocarbons from the hydrogen produced in step a) and the carbon source produced in step b), wherein at least a portion of the produced hydrocarbons are present as liquid hydrocarbons and forming, in addition to the hydrocarbons, an off-gas having or consisting essentially of hydrogen and carbon dioxide or hydrogen and carbon monoxide and optionally gaseous hydrocarbons; wherein in step c) methanol (13) is produced in the equilibrium reaction in a first process stage and methanol, unconverted hydrogen in the equilibrium reaction and unconverted carbon source in the equilibrium reaction are fed to a second process stage in which hydrocarbons (6) are produced from methanol; d) Separating the off-gas from the liquid hydrocarbon; e) Performing an off-gas recovery (8), wherein the off-gas reacts with the oxygen produced in step a) or with the oxygen and water produced in step a) or with water only, thereby forming a recovered product having or consisting essentially of water and carbon monoxide, and wherein the recovered product optionally has hydrogen, respectively.
During the exhaust gas recovery, heat is advantageously generated, which can likewise be utilized, for example, by converting said heat into electricity, for example by performing the reaction in step e) in a gas turbine, and/or by using said heat, for example, for performing evaporation and/or distillation. The process for producing hydrocarbons is advantageously low cost, as the heat is converted to electricity or utilized. The recovery of the exhaust gases can be performed by combusting the exhaust gases with oxygen produced in step a), which is particularly energy-rich due to its purity. This has the additional advantage that the oxygen produced in the electrolysis in step a) is also utilized, whereby the method is more cost-effective. Alternatively, the exhaust gas recovery may be performed by performing gasification of the exhaust gas by reaction with water. The gasification may be performed without adding oxygen or with adding oxygen generated in the electrolysis in step a). The use of oxygen in gasification also makes the process particularly inexpensive. In step e) the reaction is carried out by using the oxygen produced in step a) without using air, it being furthermore advantageously achieved that essentially no undesired substances, such as nitrogen and/or noble gases, are introduced into the process here.
In order to achieve that part of the hydrocarbons produced is present in the form of liquid hydrocarbons, cooling of the reaction products produced in step c) may be performed. The liquid hydrocarbons accumulated here can be put on the market particularly well.
In step c), it is provided that methanol is produced in the equilibrium reaction in the first process stage and that methanol, hydrogen unconverted in the equilibrium reaction and carbon source unconverted in the equilibrium reaction are fed to the second process stage, in which hydrocarbon is produced from methanol. In contrast to the process according to the prior art (see fig. 1), unconverted hydrogen and unconverted carbon source are not fed back into the synthesis of methanol (see mass flow 72). This eliminates the energy-intensive methanol separation, so that the process is particularly inexpensive. This is achieved in that unconverted hydrogen and unconverted carbon source are converted into recovered products in the offgas recovery in step e) after the second process stage. By means of the present invention, a particularly efficient methanol synthesis is achieved using the design in step c) as a two-stage process program.
In step e), different combinations of substrates, which are brought together with the exhaust gas to react, can be advantageously and flexibly realized during the execution of the exhaust gas recovery (8). This allows the exhaust gases to be brought together with the oxygen produced in step a). It is furthermore possible to bring the exhaust gases together with the oxygen produced in step a) and with water, in particular fresh water, in order to effect a reaction for the recovery of the exhaust gases. It is finally possible that the exhaust gas reacts only with water. Thus, instead of or in addition to the oxygen produced, water, in particular fresh water, reacts with the exhaust gases.
In each case, a recovered product is thus formed, which has, consists essentially of, or consists of water and carbon dioxide, and wherein the recovered product optionally has hydrogen, respectively. Thus, different reaction paths are possible on the product side.
It is particularly preferred here that water is formed in the equilibrium reaction in the first process stage, which water is not separated from methanol, unconverted hydrogen in the equilibrium reaction and unconverted carbon source in the equilibrium reaction. This also makes the method particularly inexpensive. The water formed in the equilibrium reaction of the first process stage can be separated off in step g). The hydrocarbon preferably has or preferably consists of a saturated hydrocarbon and/or olefin. The liquid hydrocarbon, in particular the saturated hydrocarbon, may be, for example, gasoline, kerosene, diesel oil and/or liquefied gas.
The specific reaction conditions for producing hydrocarbons in step c) depend on, for example, what hydrocarbons are to be produced. For example, in the production of gasoline, the pressure may be 20 to 30bar, the temperature may be 200 to 400 ℃, especially 250 to 400 ℃, and heterogeneous catalysts, such as zeolite catalysts, especially ZSM-5 catalysts, may be present.
The method preferably comprises the steps of: f) Separating water from the recovered product. Whereby the recovered product consists essentially of carbon dioxide, carbon monoxide and/or hydrogen. Whereby the recovered product has greater value than if water were still present in the recovered product.
The water separated in step f) is preferably used in step a) for electrolysis to produce hydrogen and oxygen therefrom and/or in step e) for performing a reaction with the exhaust gases. Unlike fresh water, the water separated in step f) has been demineralized. Thus, the amount of fresh water that is delivered to the process and that needs to be pre-demineralized can be reduced, making the process more cost-effective. Furthermore, the method is thus also suitable for being performed in areas lacking fresh water resources.
Preferably, the hydrocarbons in step c) are also produced from the recovered product produced in step e). Thus, advantageously, no or only little carbon is lost in the process, and the process is therefore more cost-effective. It is particularly preferred here that water is separated in step f) because the production of hydrocarbons is an equilibrium reaction and that the water contained in the recovered product will reduce the yield of liquid hydrocarbons in step c).
The heat generated in step e) is preferably partly or wholly fed to the endothermic step or steps of the process. Whereby the costs for performing the method can be reduced. The one or more endothermic steps may be, for example, evaporation and/or distillation.
The method is preferably performed continuously. In particular, a continuous mass flow of liquid hydrocarbons, a continuous mass flow of exhaust gases and a continuous mass flow of recovered products are thereby produced.
Preferably, a portion of the hydrocarbons produced in step c) is present as gaseous hydrocarbons and is also reacted in step e) with at least a portion of the gaseous hydrocarbons produced in step c). Thus, advantageously more heat is generated in step e) than is reacted with carbon dioxide and/or carbon monoxide alone and with hydrogen. This is particularly important when the heat released in step e) is insufficient to sustain the endothermic process in the process. It is particularly preferred here that the reaction is gasification.
Preferably, in step c) the portion of gaseous hydrocarbons forms part of the off-gas and/or the portion of gaseous hydrocarbons is separated from liquid hydrocarbons by distillation and subsequently mixed with the off-gas.
The gaseous hydrocarbon particularly preferably comprises C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 Hydrocarbons, or particularly preferably essentially from C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 Hydrocarbon composition. These hydrocarbons are generally of lower commercial value than hydrocarbons comprising longer chains. C (C) 1 Carbon and C 2 Carbon may be contained in the exhaust gas. It is conceivable to add C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 The hydrocarbon is at least partially dissolved in the liquid hydrocarbon. It is conceivable here to separate C in a first distillation column 1 Hydrocarbons and C 2 The hydrocarbons, and then at least partially mix with the exhaust gas. It is furthermore conceivable to separate C in a second distillation column 3 Hydrocarbons and C 4 The hydrocarbons, and then at least partially mix with the exhaust gas.
Water is also formed in step c) and the method preferably comprises the steps of: g) Water is separated from the exhaust gas and hydrocarbons. This can be done, for example, by condensation of water and phase separation from liquid hydrocarbons. It is particularly preferred here that the water separated in step g) is used in step a) for electrolysis in order to produce hydrogen and oxygen therefrom and/or in step e) in order to carry out the reaction with the exhaust gases. Unlike fresh water, the water separated in step g) has been demineralized. Thus, the amount of fresh water that is delivered to the process and that needs to be pre-demineralized can be reduced, making the process more cost-effective. Furthermore, the method is thus also suitable for being performed in areas lacking fresh water resources. If the water separated in step g) is used in step e) in order to carry out the reaction with the exhaust gases, there is furthermore the advantage that hydrocarbons which are soluble in the water are also gasified.
In step b), carbon dioxide is preferably extracted from the air, biomass is combusted, biomass is gasified and/or combustion exhaust gas is produced. Methods of extracting carbon dioxide from air are known by the term "direct air capture" (direct air capture, DAC). For example, carbon dioxide is extracted from the air by adsorption or by reaction with sodium hydroxide or potassium hydroxide, and then desorbed again, typically by input of energy, and thereby made available for subsequent processes. In order to extract carbon dioxide from air or to obtain carbon dioxide from biomass, hydrocarbons may advantageously be obtained regeneratively, that is to say without using fossil carbon sources. Alternatively, it is conceivable to use combustion exhaust gases from unavoidable combustion processes. If carbon dioxide is extracted from the air, this has the advantage that essentially no undesired substances, such as nitrogen and/or rare gases, enter the process.
The biomass is preferably burned or gasified with the oxygen produced in step a). This advantageously makes it possible to achieve that essentially no undesired substances, such as nitrogen and/or noble gases, enter the process.
The device according to the invention is configured for performing the method according to the invention or a preferred embodiment thereof.
Drawings
The invention will be further explained below with reference to the attached schematic drawings. Wherein the method comprises the steps of
FIG. 1 shows a flow chart of a conventional method;
fig. 2 shows a flow chart of a method according to the invention; and
fig. 3 shows a flow chart of a preferred embodiment of the method according to the invention.
Detailed Description
As can be seen from fig. 2, the method of producing hydrocarbons comprises the steps of: a) Performing electrolysis 3 of water, thereby generating hydrogen and oxygen; b) Producing a carbon source 4 having or consisting essentially of carbon dioxide and/or carbon monoxide; c) Producing 5 hydrocarbons from the hydrogen produced in step a) and the carbon source produced in step b), wherein at least a portion of the produced hydrocarbons are present as liquid hydrocarbons 6 and an off-gas having a composition of hydrogen, carbon dioxide and/or carbon monoxide is formed in addition to said hydrocarbons 6; d) Separating the off-gas from the liquid hydrocarbon 6; e) Waste gas recovery 8 is performed, wherein the waste gas reacts with oxygen and/or with water produced in step a), thereby forming a recovered product with carbon dioxide and/or carbon monoxide, water and optionally hydrogen.
The exhaust gas recovery may be performed, for example, by performing combustion of the exhaust gas with oxygen produced in step a). In another example, the exhaust gas recovery may be performed by gasification of the exhaust gas through reaction with water. The gasification may be performed without adding oxygen or with adding oxygen generated in the electrolysis in step a).
Fig. 2 shows that fresh water 1 can be fed to the electrolysis 3 in a mass flow 51. The hydrogen produced in step a) may be fed in a mass flow 53 to a reactor in which hydrocarbon 6 is produced in step c). The oxygen produced in step a) may be transported in a mass flow 55 separate from the mass flow 53, so that hydrogen and oxygen are not miscible.
In order to provide a carbon source in step b), a carbonaceous starting material 2 may be provided in the mass flow 52. From the mass flow 52, a carbon source may be produced, which may be transported to the reactor in mass flow 54. For example, carbon dioxide may be extracted from the air in step b), whereby the carbonaceous starting material 2 is air. In step b), biomass may be burned and/or gasified, whereby the carbonaceous starting material 2 is biomass. If biomass is burned, carbon dioxide is primarily produced; if biomass is gasified, carbon monoxide is mainly produced. It is conceivable to gasify or burn the biomass with the oxygen produced in step a). This has the advantage that no nitrogen or inert gas is thereby introduced into the process. For this purpose, the oxygen produced in step a) may be provided partially or completely in the mass flow 70, which is transported separately from the mass flow 53, so that no mixing of oxygen with hydrogen takes place. In another example, the combustion exhaust gas may be generated, inter alia, by gasification and/or combustion of fossil fuels as the carbonaceous starting material.
The production of hydrocarbons in step c) may be carried out at a reactor temperature of at least 200 ℃, in particular 250 ℃ to 400 ℃. The pressure may be from 20bar to 30bar and heterogeneous catalysts may be present, such as zeolite catalysts, especially ZSM-5 catalysts.
The off-gas separated in step d) may be provided in a mass flow 58, and may have-hydrogen,
carbon dioxide and/or carbon monoxide and,
-optionally gaseous hydrocarbons, in particular C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 Hydrocarbons, or consist essentially of:
hydrogen is used as a source of hydrogen,
carbon dioxide and/or carbon monoxide and,
-optionally gaseous hydrocarbons, in particular C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 Hydrocarbon composition. In the case of water also being formed in step c), the method may also have the following steps for this purpose: g) The water 7 is separated from the exhaust gases and the liquid hydrocarbon 6. Thereby producing a substantially pure mass flow 56 of liquid hydrocarbon 6. The separation of the water 7 from the exhaust gas may be performed by condensation and phase separation of the water 7. The water 7 separated in step g) may form a mass flow 57 and be used, for example, at least partially for the electrolysis 3 in step a) in order to generate hydrogen and oxygen therefrom. Alternatively, it is conceivable to purify and drain the water 7 in a clarification device.
In case the oxygen produced in step a) is used in step e) to perform combustion or gasification, the mass flow 55 may be mixed with the mass flow 58 in order to perform the exhaust gas recovery 8. In case gasification is performed in step e), the water 7 separated in step g) may be used at least partly in step e) in order to perform a reaction with the exhaust gases, see mass flow 67 and mass flow 65. Alternatively or in addition, the gasification in step e) can be carried out with the aid of another fresh water 11, see mass flow 66 and mass flow 65.
In step e), different combinations of substrates which come together with the exhaust gases to react can be advantageously and flexibly realized during the execution of the exhaust gas recovery 8. This allows the exhaust gases to be brought together with the oxygen produced in step a). It is furthermore possible to bring the exhaust gases together with the oxygen produced in step a) and with water, in particular fresh water, in order to effect a reaction for the recovery of the exhaust gases. It is finally possible to carry out the reaction of the exhaust gas only with water. Thus, instead of or in addition to the oxygen produced, water, in particular another fresh water 11, reacts with the exhaust gases.
In each case, a recovered product is thus formed, which has, consists essentially of, or consists of water and carbon dioxide, and wherein the recovered product optionally has hydrogen, respectively.
Thus, different reaction paths are possible on the product side.
After step e) a mass flow 59 is formed having and/or consisting essentially of carbon dioxide, carbon monoxide, hydrogen and/or water. If combustion is performed in step e), the carbon contained in the exhaust gas is substantially converted into carbon dioxide. If gasification is performed in step e), the carbon monoxide fraction in the mass flow 59 will be higher than the carbon dioxide fraction. Fig. 2 also shows that the method may comprise the steps of: f) Water 12 is separated 9 from the recovered product. Separation of water 12 may be performed by condensation of water 12. Thereby producing a mass flow 63 formed by the water 12 separated in step f). The water 12 separated in step f) may be used in step a) for electrolysis 3 (see mass flow 69) to produce hydrogen and oxygen therefrom and/or may be used in step e) to perform a reaction with the exhaust gases. The fraction of mass flow 63 that is unused in mass flow 69 may form mass flow 64. As an alternative to using the water 12 separated in step f), it is also possible to purify and drain said water 12 in a clarification device.
Figure 2 shows that in step c) hydrocarbons can also be produced from the recovered product produced in step e). To this end, downstream of the separation 9 of the water 12, a mass flow 60 with or consisting essentially of carbon dioxide, carbon monoxide and/or hydrogen may be conveyed in a direction towards the reactor. A portion of the mass flow 60 may optionally be withdrawn in the mass flow 61 as residual exhaust gas 10 in order to remove possible byproducts and thus inhibit their enrichment in the process. The mass flow 62 formed from the mass flow 60, optionally subtracted from the mass flow 61, is then fed to the reactor.
The method may be performed continuously. This means that, for example, mass flow 53, mass flow 54 and mass flow 58 are continuous, among other things.
The heat generated in step e) is preferably partly or completely transferred to the endothermic step or steps of the process, such as evaporation and/or distillation.
It is also conceivable that part of the hydrocarbons produced in step c) are present as gaseous hydrocarbons and that the reaction is also performed in step e) using at least part of the gaseous hydrocarbons 6 produced in step c). Here, in step c), the portion of gaseous hydrocarbons may be formed as part of the off-gas (which means that in fig. 2 the mass flow 58 already has the portion of gaseous hydrocarbons at its beginning) and/or the portion of gaseous hydrocarbons may be separated from the liquid hydrocarbons 6 by distillation as mass flow 68 and subsequently mixed with the off-gas, i.e. added to the mass flow 58. The gaseous hydrocarbon may have C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 Hydrocarbons or essentially of C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 Hydrocarbon composition. Here, C 1 Hydrocarbons and C 2 Hydrocarbon (hydrocarbon) optimizationOptionally at the beginning of the mass flow 58, and C 3 Hydrocarbons and C 4 The hydrocarbons are preferably present in the mass flow 68 and are mixed with the mass flow 58 after its start.
As can be seen from fig. 3, in step c) 13 methanol can be produced in the equilibrium reaction in a first process stage and the methanol, the hydrogen unconverted in the equilibrium reaction and the carbon source unconverted in the equilibrium reaction can be fed to a second process stage in which hydrocarbons are produced from methanol. To produce 13 methanol, a mass flow 78 may be provided having hydrogen and having carbon monoxide and/or carbon dioxide, or consisting essentially of hydrogen and consisting of carbon monoxide and/or carbon dioxide. In the first process stage, the reaction conditions may for example comprise: a temperature of 200 ℃ to 300 ℃, a pressure of at least 50bar, in particular 50bar to 250bar, and the ability to add metal oxide catalysts.
By producing 13 methanol, a mass flow 71 is formed, which comprises methanol and hydrogen, and carbon monoxide and/or carbon dioxide, and optionally water. The mass flow 71 is fed without separating the above-mentioned substances to the production 19 of hydrocarbons with methanol as substrate, i.e. to the second process stage. In the second process stage, for example, the pressure may be from 20bar to 30bar, the temperature may be from 200 ℃ to 400 ℃, in particular from 250 ℃ to 400 ℃, and heterogeneous catalysts, such as zeolite catalysts, in particular ZSM-5 catalysts, may be present. Steps d) and e) are performed similarly to fig. 1. In addition, the exhaust gas may also have C 1 Hydrocarbons to C 4 And (3) hydrocarbons.
It is conceivable that water is formed in the equilibrium reaction of the first process stage (if carbon dioxide is used as substrate for the production of methanol) which is fed to the second process stage. The water is not separated until step d).
The process is particularly advantageously operated with methanol as a preferred product from methanol synthesis 13 for the production of hydrocarbons. The methanol can in turn be used as a valuable starting material (substrate) or intermediate for the production of further high value liquid hydrocarbons of (19).
Where the hydrocarbon contains C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 In the case of hydrocarbons, if the process is carried out at a site of the same refinery, it is possible, for example, to use C particularly simply 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 And (3) hydrocarbons. C (C) 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 Hydrocarbons can be taken as substrates for use in refineries. The refinery may be, for example, a steam cracker. Ethylene can be produced in a steam cracker, which has high commercial value.
If the method is performed at a location where other chemical or pharmaceutical industry equipment is also available, the heat generated in step e) can also be put on the market. The heat generated in step e) can be utilized, for example, in order to perform endothermic processes, such as evaporation or distillation, in other devices.
The device is configured to perform the method.
Claims (14)
1. A process for producing hydrocarbons (6), the process comprising the steps of:
a) Performing electrolysis (3) of water, thereby generating hydrogen and oxygen;
b) Producing a carbon source (4) having or consisting essentially of carbon dioxide and carbon monoxide;
c) Producing (5) the hydrocarbon (6) from the hydrogen produced in step a) and the carbon source produced in step b), wherein at least part of the produced hydrocarbon is present as liquid hydrocarbon and an off-gas is formed in addition to the hydrocarbon (6), the off-gas having or consisting essentially of hydrogen, carbon dioxide and carbon monoxide, wherein in step c) methanol is produced (13) in an equilibrium reaction and the methanol, the hydrogen unconverted in the equilibrium reaction and the carbon source unconverted in the equilibrium reaction are transported to a second process stage in which the hydrocarbon (6) is produced from the methanol;
d) Separating the off-gas from the liquid hydrocarbon (6);
e) Performing an off-gas recovery (8) in which the reaction of the off-gas with the oxygen produced in step a) or with the oxygen and water produced in step a) or the reaction of the off-gas with water is performed, thereby forming a recovered product having or consisting essentially of water, carbon dioxide and carbon monoxide, and wherein the recovered product optionally has hydrogen, respectively.
2. A process according to claim 1, wherein in step c) water is formed in the equilibrium reaction which is fed to the second process stage.
3. The method according to claim 1 or 2, having the steps of:
f) Separating (9) water (12) from the recovered product.
4. A method according to claim 3, wherein the water (12) separated in step f) is used in step a) for electrolysis (3) to produce hydrogen and oxygen therefrom and/or in step e) for performing a reaction with exhaust gases.
5. A process according to any one of claims 1 to 4, wherein in step c) the hydrocarbon (6) is also produced from the recovered product produced in step e).
6. The method of any one of claims 1 to 5, wherein the method is performed continuously.
7. The method according to any one of claims 1 to 6, wherein in step c) a part of the produced hydrocarbons is present as gaseous hydrocarbons and in step e) the reaction is also performed using at least a part of the gaseous hydrocarbons produced in step c).
8. Method according to claim 7, wherein in step c) the part of the gaseous hydrocarbon is formed as part of the exhaust gas and/or the part of the gaseous hydrocarbon is separated from the liquid hydrocarbon (6) by distillation and subsequently mixed with the exhaust gas.
9. The method of claim 7 or 8, wherein the moiety has C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 Hydrocarbons or essentially of C 1 Hydrocarbons, C 2 Hydrocarbons, C 3 Hydrocarbons and/or C 4 Hydrocarbon composition.
10. The method according to any one of claims 1 to 9, wherein water is also formed in step c) and the method comprises the steps of:
g) -separating the water (7) from the exhaust gas and the hydrocarbons (6).
11. Method according to claim 10, wherein the water (7) separated in step g) is used in step a) for electrolysis (3) for generating hydrogen and oxygen therefrom and/or in step e) for performing a reaction with the exhaust gases.
12. The method according to any one of claims 1 to 11, wherein in step b) carbon dioxide is extracted from the air, biomass is combusted, biomass is gasified and/or combustion exhaust gas is produced.
13. The method according to claim 12, wherein the biomass is combusted or gasified by means of oxygen produced in step a).
14. Apparatus for performing the method according to any one of claims 1 to 13.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102021204337.2 | 2021-04-30 | ||
| EP21181829.9A EP4083258A1 (en) | 2021-04-30 | 2021-06-25 | Method and system for the production of hydrocarbons |
| EP21181829.9 | 2021-06-25 | ||
| PCT/EP2022/057983 WO2022228793A1 (en) | 2021-04-30 | 2022-03-25 | Method and system for producing hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117242211A true CN117242211A (en) | 2023-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280031224.1A Pending CN117242211A (en) | 2021-04-30 | 2022-03-25 | Method and apparatus for producing hydrocarbons |
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| Country | Link |
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| CN (1) | CN117242211A (en) |
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