Process and apparatus for converting carbon dioxide to olefins

Abstract

A process and apparatus for converting carbon dioxide to hydrocarbons. Carbon dioxide and coke react in a reaction zone to produce carbon monoxide. The carbon monoxide and hydrogen streams are reacted to produce methanol. Methanol is reacted in the reaction zone to produce ethylene and propylene. Hydrogen and oxygen may be generated in an electrolysis zone that separates water into hydrogen and oxygen.

Description

[0001] Priority declaration

[0002] This application claims priority to U.S. patent application serial number 17 / 817,418 filed on August 4, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention generally relates to methods and apparatus for converting carbon dioxide to olefins. Background Art

[0004] Carbon dioxide is produced in a variety of industrial processes and is typically emitted into the atmosphere, however, since carbon dioxide is considered a greenhouse gas, it is desirable and generally necessary to reduce the amount of carbon dioxide emitted into the atmosphere.

[0005] While CO2 capture technology is available, there are limited options for using the captured CO2. Therefore, the captured CO2 requires carbon sequestration technology. Unfortunately, current transportation and storage infrastructure still lacks the capacity to facilitate large-scale adoption. In addition, the CO2 financial incentives currently available in some countries are not yet at a level that makes CO2 capture economically feasible or desirable.

[0006] Therefore, more effective and efficient ways to deal with the generated carbon dioxide are desired. Summary of the invention

[0007] One or more methods and apparatuses for converting carbon dioxide into olefins have been invented. The inventive method consumes the captured carbon dioxide (thereby solving the carbon dioxide usage problem) by converting coke into synthesis gas to generate carbon monoxide. The carbon monoxide can then be used for methanol synthesis, and then light olefins are produced from the produced methanol.

[0008] The method and apparatus of the present invention include an electrolysis zone which can consume water generated by light olefin production to further increase the circularity of the solution. The green hydrogen produced from the electrolysis zone can be used for methanol synthesis. A power recovery turbine can be used to generate electricity which can then be used to supply the electrolysis section. This electricity can be considered blue power in view of the capture and use of carbon dioxide.

[0009] The method and apparatus of the present invention provide a green and sustainable outlet for coke, enable the production of olefins from green coal, and help solve the problem of carbon dioxide generation.

[0010] Thus, the present invention can be generally characterized as providing, in at least one aspect, a method for converting carbon dioxide by: reacting carbon dioxide with coke to produce carbon monoxide in a first reaction zone operated under suitable conditions; generating hydrogen from water in an electrolysis zone operated under suitable conditions; and reacting carbon monoxide from the first reaction zone with hydrogen from the electrolysis zone to produce methanol in a second reaction zone operated under suitable conditions.

[0011] The present invention can also be broadly characterized as providing a method for converting carbon dioxide to hydrocarbons by: passing coke and a stream containing carbon dioxide to a first reaction zone, the first reaction zone being operated under suitable conditions to produce carbon monoxide, wherein the effluent from the first reaction zone contains carbon monoxide; passing a stream containing water to an electrolysis zone, the electrolysis zone receiving electrical energy and the electrolysis zone being configured to provide a stream containing hydrogen; and passing the effluent stream from the first reaction zone and the stream containing hydrogen to a second reaction zone, the second reaction zone being operated under suitable conditions to produce methanol, wherein the effluent from the second reaction zone contains methanol.

[0012] In another third aspect, the present invention can be broadly characterized as providing a system for converting carbon dioxide to hydrocarbons, the system having at least: a first reaction zone, the first reaction zone being configured to: receive coke and a feed stream comprising carbon dioxide, and when operated under appropriate conditions, produce an effluent comprising carbon monoxide; an electrolysis zone, the electrolysis zone being configured to receive a feed stream comprising water and electrical energy and being configured to provide a feed stream comprising hydrogen; and a second reaction zone, the second reaction zone being configured to: receive the effluent from the first reaction zone and a feed stream comprising hydrogen, and when operated under appropriate conditions, produce methanol, wherein the effluent from the second reaction zone comprises methanol.

[0013] Further aspects, embodiments and details of the invention (all of which may be combined in any manner) are set forth in the following detailed description of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] One or more exemplary embodiments of the present invention will be described below in conjunction with the following drawings, in which:

[0015] Figure 1 shows apparatus and process flow diagrams according to one or more embodiments of the present invention; and

[0016] Figure 2 A first reaction zone is shown that may be used in one or more embodiments of the present invention. DETAILED DESCRIPTION

[0017] As mentioned above, invented the method and apparatus for converting carbon dioxide into olefins.Usually, coke from various process units can be fed to fluidized bed reactor in the form of powder or slurry, which contacts with carbon dioxide from other sources.Sand or other equivalent materials can be used for the circulation between reactor and regenerator, and this regenerator will carry the required heat for realizing Boudouard reaction (it will be subjected to carbon dioxide and carbon monoxide ratio of 2:1 to 6:1 via continuous carbon dioxide recirculation).The reactor effluent containing carbon monoxide and carbon dioxide is mixed with hydrogen from water electrolysis zone to generate synthesis gas.Reactor effluent (synthesis gas) is used for methanol synthesis, and methanol can be converted into light olefins (propylene / ethylene) subsequently.The water generated from the conversion of methanol to olefins is circulated back to the water electrolysis zone.The carbon dioxide from the regenerator in methanol to olefin conversion can be recycled back in the first reactor, and the oxygen produced by water electrolysis can be sent to the regenerator in methanol to conversion.

[0018] With these general principles in mind, one or more detailed acts of the invention will now be described with the understanding that the description is not intended to be limiting.

[0019] like Figure 1 and Figure 2 As shown, in a first reaction zone 10, coke 12 is reacted with a stream containing carbon dioxide 14 under suitable conditions to produce carbon monoxide. The conditions include a temperature of at least 760°C (1400°F) and a pressure range of 0.1 barg to 10 barg, preferably 0.1 barg to 5 barg. Sources of coke may include, for example, delayed cokers, coal, solvent deasphalting, steam cracking tars, pyoils, and vacuum fractionation residues.

[0020] In the first reaction zone, carbon monoxide is produced by the Boudouard reaction:

[0021] C + CO2 → 2 CO (1).

[0022] exist Figure 1 In the embodiment of the present invention, the first reaction zone 10 includes a reaction vessel or reactor 16 and a regeneration vessel 18. Thus, a fuel 20 and an oxygen stream 22 (e.g., air) are conveyed to a combustion zone 24 to generate heat. An effluent stream 26 from the combustion zone 24 transfers heat to the regeneration vessel 18, and more specifically to a heat supply medium contained in the regeneration vessel 18. The heat supply medium may be sand or any solid powder with high thermal conductivity that is mechanically and thermally stable under the reaction conditions in a fluidized bed state.

[0023] A hot heat supply medium 28 may be delivered to the reaction vessel 16. The reaction vessel 16 receives the carbon dioxide 14 and the coke 12. The hot heat supply medium 28 provides heat for the Boudouard reaction. The effluent 30 from the first reaction zone 10 contains carbon monoxide. The cold heat supply medium 32 may be returned to the regeneration vessel 18. A pollutant removal zone 34 may be included to remove pollutants from the effluent 30 containing carbon monoxide, such as by desulfurization, denitrification, particulate removal.

[0024] The flue gas 36 from the regeneration vessel 18 may be passed to a power recovery turbine 38. In the power recovery turbine 38, the pressure of the flue gas 36 may be reduced while generating electricity 39 (as discussed below). After water and other gases are removed in the pollutant removal zone 34, the flue gas 36 containing carbon dioxide may then be passed to the first reaction zone 10 as part of the stream containing carbon dioxide 14.

[0025] exist Figure 2 In the embodiment of the present invention, the first reaction zone 10' includes a first reaction vessel 16a and a second reaction vessel 16b. In the first reaction vessel 16a, the coke 12 is burned using oxygen 22 to generate carbon dioxide. A stream containing carbon dioxide 14 is sent directly to the second reaction vessel 16b at a high temperature. In the second reaction vessel 16b, the coke 12 will react with the carbon dioxide to produce an effluent 30 containing carbon monoxide by a Boudouard reaction. The heat required for the Boudouard reaction is provided by burning the coke 12 in the first reaction vessel 16a. The outlet of the first reactor can be 1,000°C (1,832°F). It is expected that the outlet of the second reactor will be 760°C (1,400°F) or higher because the Boudouard reaction tends to stop below 760°C. Figure 2 The rest of Figure 1 same.

[0026] Therefore, returning to Figure 1 , the effluent 30 from the first reaction zone 10, 10' is sent to the second reaction zone 40, which is operated under suitable conditions to produce methanol. In particular, the second reaction zone 40 receives the effluent 30 containing carbon monoxide and hydrogen 42 and produces methanol by the following reaction:

[0027] CO + 2H2 → CH3OH (2).

[0028] In addition, the effluent 30 from the first reaction zone 10, 10' will also include carbon dioxide. Therefore, in the second reaction zone 40, carbon dioxide can also be converted into methanol in the following reaction:

[0029] CO2 + 3H2 → CH3OH + H2O (3).

[0030] Suitable conditions for second reaction zone 40 include operating temperatures between 250°C and 300°C (482°F and 572°F) and pressures between 50 bar and 100 bar. Reactions (2) and (3) above typically employ copper-zinc oxide based catalysts.

[0031] Hydrogen 42 consumed in second reaction zone 40 is produced in electrolysis zone 44, which receives electricity 45 and operates under suitable conditions to generate hydrogen 42 and oxygen 46 from water 48. Electricity 39 from power recovery turbine 38 may be sent to electrolysis zone 44. Oxygen 46 from electrolysis zone 44 may be used in first reaction zone 10 and / or stream 22 as described below.

[0032] The effluent 50 from the second reaction zone 40 may be passed to a third reaction zone 52. In the third reaction zone 52, the methanol produced in the second reaction zone 40 may be converted to olefins, such as light olefins, including ethylene and propylene, in the following reaction:

[0033] 2 CH3OH →CH3OCH3 +H2O (4)

[0034] 2 CH3OCH3 → C2H4 + H2O (5)

[0035] 3 CH3OCH3 → C3H6 + 2 H2O (6).

[0036] Although not shown, the third reaction zone 52 may include a reactor and a regenerator. The methanol produced from the second reaction zone 40 is transferred to the reactor, which may be a fluidized bed catalytic reactor containing a catalyst configured to produce olefins and water by reactions (4), (5) and (6). A fractionation section may be included downstream to separate the effluent into an olefin stream 54 and a water stream 56. The water stream 56 may be recycled back to the electrolysis zone 44.

[0037] The coking catalyst from the reactor can be sent to the regenerator to remove the coke by combustion. Oxygen 46 from the electrolysis zone 44 can be used for this. In addition, the gaseous flue gas 58 from the regenerator will contain carbon dioxide. Therefore, after water and other gases are separated in the pollutant removal zone 34, the gaseous flue gas 58 can be recycled back to the first reaction zone 10, 10 '. It is also expected that the gaseous flue gas 58 from the regenerator can be transported to the power recovery turbine 38 installed in the flue gas 36 from the first reaction zone 10, 10 '.

[0038] experiment

[0039] In a hypothetical economic analysis of the process according to the invention, in addition to generating revenue from the production of light olefins, the invention generates marketable carbon dioxide credits. Thus, the invention provides an economically desirable process and apparatus for reducing emissions and sequestering carbon dioxide.

[0040] Those of ordinary skill in the art will recognize and appreciate that various other components such as valves, pumps, filters, coolers, etc. are not shown in the accompanying drawings because it is believed that their details are well within the knowledge of those of ordinary skill in the art and their description is not necessary for the practice or understanding of the embodiments of the present invention.

[0041] Any of the above-mentioned pipelines, conduits, units, equipment, containers, surrounding environments, zones, or the like may be equipped with one or more monitoring components, including sensors, measuring devices, data capture devices, or data transmission devices. Signals, process or state measurements and data from the monitoring components can be used to monitor conditions in, around, and related to the process equipment. The signals, measurements, and / or data generated or recorded by the monitoring components can be collected, processed, and / or transmitted via one or more networks or connections, which can be private or public, general or dedicated, direct or indirect, wired or wireless, encrypted or unencrypted, and / or combinations thereof; the present specification is not intended to be limiting in this regard.

[0042] The signals, measurements, and / or data generated or recorded by the monitoring components may be transmitted to one or more computing devices or systems. The computing device or system may include at least one processor and a memory storing computer-readable instructions that, when executed by at least one processor, cause one or more computing devices to perform a method that may include one or more steps. For example, one or more computing devices may be configured to receive data related to at least one piece of equipment associated with the method from one or more monitoring components. One or more computing devices or systems may be configured to analyze the data. Based on the data analysis, one or more computing devices or systems may be configured to determine one or more recommended adjustments to one or more parameters of one or more methods described herein. One or more computing devices or systems may be configured to transmit encrypted or unencrypted data, which includes one or more recommended adjustments to one or more parameters of one or more methods described herein.

[0043] Specific implementation plan

[0044] While the following is described in conjunction with specific embodiments, it should be understood that this description is intended to illustrate and not to limit the scope of the foregoing description and the appended claims.

[0045] The first embodiment of the present invention is a method for converting carbon dioxide, the method comprising: reacting carbon dioxide with coke to produce carbon monoxide in a first reaction zone operated under suitable conditions; generating hydrogen from water in an electrolysis zone operated under suitable conditions; and reacting carbon monoxide from the first reaction zone with hydrogen from the electrolysis zone to produce methanol in a second reaction zone operated under suitable conditions. One embodiment of the present invention is one, any or all of the first embodiment of this paragraph to the previous embodiment of this paragraph, the method further comprising: converting methanol from the second reaction zone into light olefins in a third reaction zone operated under suitable conditions. One embodiment of the present invention is one, any or all of the first embodiment of this paragraph to the previous embodiment of this paragraph, wherein the third reaction zone provides an olefin stream and a gaseous stream containing carbon dioxide. One embodiment of the present invention is one, any or all of the first embodiment of this paragraph to the previous embodiment of this paragraph, wherein the gaseous stream containing carbon dioxide is recycled to the first reaction zone. One embodiment of the present invention is one, any one or all of the first embodiment of this paragraph to the previous embodiments of this paragraph, and the method further comprises: in a third reaction zone operated under suitable conditions, converting methanol from the second reaction zone into light olefins, wherein oxygen is transferred to the third reaction zone, and wherein in the electrolysis zone, oxygen is produced. One embodiment of the present invention is one, any one or all of the first embodiment of this paragraph to the previous embodiments of this paragraph, wherein the first reaction zone comprises a reaction vessel and a regeneration vessel, wherein a heat supply medium circulates between the reaction vessel and the regeneration vessel. One embodiment of the present invention is one, any one or all of the first embodiment of this paragraph to the previous embodiments of this paragraph, wherein the first reaction zone comprises a first reaction vessel and a second reaction vessel, the first reaction vessel being configured to receive the coke, and the second reaction vessel being configured to receive an effluent stream from the first reaction vessel.

[0046] A second embodiment of the present invention is a method for converting carbon dioxide into hydrocarbons, the method comprising: conveying coke and a stream comprising carbon dioxide to a first reaction zone, the first reaction zone operating under suitable conditions to produce carbon monoxide, wherein the effluent from the first reaction zone comprises carbon monoxide; conveying a stream comprising water to an electrolysis zone, the electrolysis zone receiving electrical energy and the electrolysis zone being configured to provide a stream comprising hydrogen; and conveying the effluent stream from the first reaction zone and a stream comprising hydrogen to the second reaction zone, the second reaction zone operating under suitable conditions to produce methanol, wherein the effluent from the second reaction zone comprises methanol. One embodiment of the present invention is one, any or all of the second embodiment of this paragraph to the previous embodiment of this paragraph, wherein the first reaction zone comprises a reaction vessel and a regeneration vessel, wherein a heat supply medium circulates between the reaction vessel and the regeneration vessel. One embodiment of the present invention is one, any or all of the second embodiment of this paragraph to the previous embodiment of this paragraph, the method further comprising: in a third reaction zone operating under suitable conditions, converting methanol from the second reaction zone into light olefins. One embodiment of the present invention is one, any or all of the second embodiment of this paragraph to the previous embodiment of this paragraph, wherein the electrolysis zone provides a stream containing oxygen, and wherein the stream containing oxygen is conveyed to the third reaction zone. One embodiment of the present invention is one, any or all of the second embodiment of this paragraph to the previous embodiment of this paragraph, wherein the third reaction zone provides an olefin stream and a gaseous stream containing carbon dioxide, and the method further comprises conveying the gaseous stream containing carbon dioxide to the first reaction zone. One embodiment of the present invention is one, any or all of the second embodiment of this paragraph to the previous embodiment of this paragraph, and the method further comprises: before conveying the gaseous stream containing carbon dioxide provided by the third reaction zone to the first reaction zone, conveying the gaseous stream containing carbon dioxide to a power recovery turbine to generate electricity. One embodiment of the present invention is one, any or all of the second embodiment of this paragraph to the previous embodiment of this paragraph, wherein the third reaction zone also provides a water stream, and the method further comprises conveying the water stream to the electrolysis zone.

[0047] The third embodiment of the present invention is a system for converting carbon dioxide into hydrocarbons, the system comprising: a first reaction zone, the first reaction zone is configured to: receive coke and a stream containing carbon dioxide, and when operating under suitable conditions, produce an effluent containing carbon monoxide; an electrolysis zone, the electrolysis zone is configured to receive a stream containing water and electrical energy and is configured to provide a stream containing hydrogen; and a second reaction zone, the second reaction zone is configured to: receive an effluent from the first reaction zone and a stream containing hydrogen, and when operating under suitable conditions, produce methanol, wherein the effluent from the second reaction zone contains methanol. One embodiment of the present invention is one, any one or all of the third embodiment of this paragraph to the previous embodiment of this paragraph, the system further comprising a third reaction zone, the third reaction zone is configured to convert the methanol from the second reaction zone into light olefins when operating under suitable conditions. One embodiment of the present invention is one, any one or all of the third embodiment of this paragraph to the previous embodiment of this paragraph, wherein the electrolysis zone is configured to provide a stream containing oxygen to the third reaction zone. One embodiment of the present invention is one, any or all of the third embodiment of this paragraph to the previous embodiment of this paragraph, wherein the first reaction zone comprises a reaction vessel and a regeneration vessel, wherein a heat supply medium circulates between the reaction vessel and the regeneration vessel. One embodiment of the present invention is one, any or all of the third embodiment of this paragraph to the previous embodiment of this paragraph, wherein the system further comprises a power recovery turbine, wherein the power recovery turbine is configured to generate electricity from flue gas from the regeneration vessel, wherein the electricity generated by the power recovery turbine is provided to the electrolysis zone. One embodiment of the present invention is one, any or all of the third embodiment of this paragraph to the previous embodiment of this paragraph, wherein the first reaction zone comprises a first reaction vessel and a second reaction vessel, wherein the first reaction vessel is configured to receive the coke, and the second reaction vessel is configured to receive an effluent stream from the first reaction vessel. One embodiment of the present invention is one, any or all of the third embodiment of this paragraph to the previous embodiment of this paragraph, wherein the system further comprises a pipeline configured to recycle water from the third reaction zone to the electrolysis zone.

[0048] Although there is no further detailed description, it is believed that those skilled in the art can utilize the present invention to the greatest extent by using the foregoing description and can easily determine the essential characteristics of the present invention without departing from the spirit and scope of the present invention to make various changes and modifications of the present invention and adapt it to various usages and conditions. Therefore, the aforementioned preferred specific embodiments should be understood as merely illustrative and not to limit the rest of the present disclosure in any way, and are intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0049] In the foregoing, all temperatures are set forth in degrees Celsius and all parts and percentages are by weight unless otherwise indicated.

[0050] Although at least one exemplary embodiment has been presented in the foregoing specific embodiments of the present invention, it should be understood that there are a large number of variations. It should also be understood that an exemplary embodiment or multiple exemplary embodiments are only examples and are not intended to limit the scope, applicability or configuration of the present invention in any way. On the contrary, the foregoing specific embodiments will provide a convenient roadmap for those skilled in the art to implement the exemplary embodiments of the present invention, and it should be understood that various changes can be made to the functions and arrangements of the elements described in the exemplary embodiments without departing from the scope of the present invention as set forth in the attached claims and their legal equivalents.

Claims

1. A method for converting carbon dioxide, the method comprising: reacting carbon dioxide (14) with coke (12) in a first reaction zone (10, 10') operated under suitable conditions to produce carbon monoxide (30); generating hydrogen (42) from water (48) in an electrolysis zone (44) operated under suitable conditions, and In a second reaction zone (40) operated under suitable conditions, carbon monoxide (30) from the first reaction zone (10, 10') is reacted with hydrogen (42) from the electrolysis zone (44) to produce methanol (50).

2. The method according to claim 1, further comprising: The methanol (50) from the second reaction zone (40) is converted to light olefins (54) in a third reaction zone (52) operated under suitable conditions.

3. The process of claim 2, wherein the third reaction zone (52) provides an olefin stream (54) and a gaseous stream (58) comprising carbon dioxide.

4. The process according to claim 3, wherein the gaseous stream (58) comprising carbon dioxide is recycled to the first reaction zone (10, 10').

5. The method according to claim 1, further comprising: converting the methanol (50) from the second reaction zone (40) into light olefins (54) in a third reaction zone (52) operated under suitable conditions, wherein oxygen (46) is passed to the third reaction zone (52), and wherein oxygen (46) is produced in the electrolysis zone (44).

6. A method according to any one of claims 1 to 5, wherein the first reaction zone (10) comprises a reaction vessel (16) and a regeneration vessel (18), wherein a heat supply medium (28, 32) circulates between the reaction vessel (16) and the regeneration vessel (18).

7. A method according to any one of claims 1 to 5, wherein the first reaction zone (10') comprises a first reaction vessel (16a) and a second reaction vessel (a6b), the first reaction vessel (16a) being configured to receive the coke (12), and the second reaction vessel (16b) being configured to receive an effluent material flow (14) from the first reaction vessel (16a).

8. A system for converting carbon dioxide into hydrocarbons, the system comprising: a first reaction zone (10, 10') configured to receive coke (12) and a stream comprising carbon dioxide (14) and, when operated under suitable conditions, to produce an effluent (30) comprising carbon monoxide; an electrolysis zone (44) configured to receive a stream comprising water (48) and electrical energy (39, 45) and configured to provide a stream comprising hydrogen (42); and A second reaction zone (40) is configured to receive the effluent (30) from the first reaction zone (10, 10') and a stream comprising hydrogen (42), and when operated under suitable conditions, produces methanol, wherein the effluent (50) from the second reaction zone (40) comprises methanol.

9. The system according to claim 8, further comprising: A third reaction zone (52) configured to convert methanol (50) from the second reaction zone (40) into light olefins (54) when operated under suitable conditions.

10. The system according to claim 8 or 9, further comprising: A power recovery turbine (38) is configured to generate electricity (39) from the gaseous stream (36), wherein the electricity (39) generated by the power recovery turbine (38) is provided to the electrolysis zone (44).

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