Abstract
A method for producing green olefins and green gasoline from renewable sources, the method including: providing CO.sub.2 and hydrogen as feed to produce methanol in a methanol reactor, to produce an MTO reaction effluent, reacting the MTO reaction effluent in a plurality of separation columns to separate hydrocarbons, wherein the plurality of separation columns includes a Deethanizer column, a Depropanizer column, and a Debutanizer column, hydrogenating a fraction of separated hydrocarbons in the Debutanizer column with the hydrogen in a hydrogenation reactor, wherein the fraction of separated hydrocarbons from the Debutanizer column includes C.sub.5+ hydrocarbons; producing the green gasoline and Liquefied Petroleum Gas (LPG) by stabilizing the hydrogenated hydrocarbons in a gasoline stabilizer column; and producing the olefins by separating ethylene from C.sub.2 hydrocarbons using a C.sub.2 splitter column and by separating propylene from C.sub.3 hydrocarbons using a C.sub.3 splitter column.
Claims
1. A method for producing olefins and gasoline from renewable sources, comprising: providing carbon dioxide and hydrogen as feed to produce methanol in a methanol reactor, wherein the hydrogen is obtained from a water electrolyzer; reacting the methanol in a Methanol-to-Olefin (MTO) reactor to produce a MTO reaction effluent comprising olefinic and non-olefinic hydrocarbons and water, wherein the water in the MTO reaction effluent is used at least partially as feed for the water electrolyzer, wherein non-converted carbon dioxide from the methanol reactor is directed at least partially into the MTO reactor; treating the MTO reaction effluent in a plurality of separation columns to separate the hydrocarbons, wherein the plurality of separation columns comprises a Deethanizer column, a Depropanizer column, a Debutanizer column, a C.sub.2 splitter column, and a C.sub.3 splitter column, wherein the separation of the hydrocarbons from the MTO reaction effluent comprises (i) separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons at the Deethanizer column, (ii) separating ethylene from the C.sub.2 hydrocarbons at the C.sub.2 splitter column, (iii) separating C.sub.3 hydrocarbons from C.sub.4+ hydrocarbons at the Depropanizer column, (iv) separating propylene from the C.sub.3 hydrocarbons at the C.sub.3 splitter column, and (v) separating C.sub.4 hydrocarbons as a Debutanizer overhead fraction at the Debutanizer column, wherein a fraction of the separated hydrocarbons settles at a bottom of the Debutanizer column as a Debutanizer bottom fraction after separation, wherein the Debutanizer bottom fraction comprises C.sub.5+ hydrocarbons; hydrogenating at least a part of the Debutanizer bottom fraction with the hydrogen obtained from the water electrolyzer in a hydrogenation reactor to obtain a hydrogenated Debutanizer bottom fraction; routing out at least a part of the hydrogenated Debutanizer bottom fraction as gasoline product, or separating Liquefied Petroleum Gas (LPG) from the hydrogenated Debutanizer bottom fraction in a gasoline stabilizer column, routing out a LPG product as a gasoline stabilizer column overhead fraction, and routing out a stabilized gasoline product as a gasoline stabilizer column bottom fraction; and routing out an olefin product, comprising propylene.
2. The method according to claim 1, wherein the separation of hydrocarbons in the plurality of separation columns comprises: (i) treating the MTO reaction effluent in the Deethanizer column, wherein the Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene, and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons, and (ii) treating the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons in the Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene, and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons, wherein the Depropanizer bottom fraction rich in C.sub.4+ hydrocarbons comprises 20-50% of C.sub.4 olefins and 50 to 80% of C.sub.4 paraffins, wherein the Depropanizer bottom fraction is at least partially directed to the hydrogenation reactor for hydrogenation.
3. The method according to claim 1, wherein, when the plurality of separation columns comprises a dehexanizer column, the separation of hydrocarbons in the plurality of separation columns comprises (i) treating the Debutanizer bottom fraction that is rich in C.sub.5+ hydrocarbons in the Dehexanizer column to produce a Dehexanizer overhead vapor fraction that is rich in hexane and hexene, and a Dehexanizer bottom fraction that is rich in C.sub.7+ hydrocarbons, wherein the Dehexanizer bottom fraction is directed to the hydrogenation reactor for hydrogenation.
4. The method according to claim 1, wherein the C.sub.2 splitter column separates ethylene from ethane, wherein the C.sub.3 splitter column separates propylene from propane, wherein the ethylene and propylene are comprised in the overhead fractions of the C.sub.2 splitter column and the C.sub.3 splitter column, and wherein the propane is directed at least partially to the hydrogenation reactor.
5. The method according to claim 4, wherein at least a part of the ethylene is converted into ethanol and added to the gasoline product or stabilized gasoline product to increase the Research Octane Number (RON) and/or the Motor Octane Number (MON) of the gasoline.
6. The method according to claim 2, wherein the method comprises scrubbing the carbon dioxide from the MTO reaction effluent using a carbon dioxide scrubber, wherein at least a part of the scrubbed carbon dioxide is provided as feed into the methanol reactor.
7. The method according to claim 1, wherein, when the plurality of separation columns comprises a Demethanizer column, the method comprises directing the Deethanizer overhead vapor fraction into the Demethanizer column to produce an overhead fraction comprising methane.
8. The method according to claim 7, wherein the method comprises directing at least a part of the overhead fraction from the Demethanizer column into the methanol reactor.
9. The method according to claim 1, wherein the method comprises recycling at least one element, selected from the following group: (i) the Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons, (ii) the Debutanizer bottom fraction that is rich in C.sub.5+ hydrocarbons, (iii) the ethylene from the C.sub.2 splitter column overhead fraction, (iv) the propane from the C.sub.3 splitter column overhead fraction, at least partially into the MTO reactor.
10. The method according to claim 1, wherein the method comprises quenching the MTO reaction effluent by treating the MTO reaction effluent with water before separating the MTO reaction effluent in the plurality of separation columns, wherein the water after quenching is directed at least partially into the water electrolyzer.
11. The method according to claim 1, wherein the carbon dioxide used as the feed to produce methanol is free of sulfur components and amines.
12. The method according to claim 1, wherein the methanol produced in the methanol reactor is purified in a distillation column which is operated under a pressure ranging between 25 bar to 125 bar, and a temperature ranging between 200° C. and 350° C.
13. The method according to claim 1, wherein the methanol produced in the methanol reactor is a methanol-water mixture comprising in a range of 62 to 66 weight by percentage (wt-%) of methanol and about 34 to 38 weight by percentage (wt-%) of water.
14. The method according to claim 13, wherein the methanol-water mixture is reacted directly without any treatment or separation in the MTO reactor.
15. The method according to claim 1, wherein the methanol from the methanol reactor is separated from the water depending on an amount of carbon dioxide available for the reaction to convert oxygenate in the MTO reactor.
16. The method according to claim 1, wherein the method comprises directing a purge gas with carbon dioxide and H.sub.2 obtained from the methanol reactor into the MTO reactor.
17. The method according to claim 1, wherein the non-converted carbon dioxide that is directed into the MTO reactor optimizes a partial pressure of reactants in the MTO reactor and increases a lifetime of a catalyst included in the isothermal MTO reactor.
18. The method according to claim 1, wherein at least a part of the carbon dioxide is used as a diluting agent for the hydrogenation of hydrocarbons in the hydrogenation reactor.
19. The method according to claim 1, wherein carbon dioxide and/or hydrogen are used as diluting agents during oxidative regeneration of the catalyst in the MTO reactor.
20. The method according to claim 1, wherein the method includes performing the MTO reaction in the MTO reactor at a temperature in a range of 400 to 550° C. and at a pressure in a range of 0.2 to 5 bara to increase the C.sub.3 hydrocarbons yield in the MTO reaction effluent.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] The summary above, as well as the following detailed description of illustrative embodiments, is better understood when read in conjunction with the appended drawings. To illustrate the present disclosure, exemplary constructions of the disclosure are shown in the drawings. However, the present disclosure is not limited to specific methods and instrumentalities disclosed herein. Moreover, those in the art will understand that the drawings are not to scale. Wherever possible, the same elements have been indicated by identical numbers. Embodiments of the present disclosure will now be described, by way of example only, with reference to the following diagrams wherein:
[0035] FIG. 1 is a schematic illustration of an apparatus for producing olefins and gasoline from renewable sources according to an embodiment of the present disclosure;
[0036] FIG. 2 is a schematic illustration of a once-through process for producing olefins and gasoline from renewable sources utilizing scrubbed CO.sub.2 as a feed for producing methanol and Methanol-to-Olefin (MTO) reaction according to an embodiment of the present disclosure;
[0037] FIG. 3 is a schematic illustration of a once-through process for producing olefins and gasoline from renewable sources utilizing scrubbed CO.sub.2 as a feed for Methanol-to-Olefin (MTO) reaction according to an embodiment of the present disclosure;
[0038] FIG. 4 is a schematic illustration of a once-through process for producing olefins and gasoline from renewable sources comprising converting green ethylene into ethyl alcohol to increase Research Octane Number (RON) and Motor Octane Number (MON) of green gasoline according to an embodiment of the present disclosure;
[0039] FIG. 5 is a schematic illustration of a process with recycling for producing olefins and gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction into an isothermal Methanol-to-Olefin (MTO) reactor and utilizing scrubbed CO.sub.2 as a feed for Methanol-to-Olefin (MTO) reaction according to an embodiment of the present disclosure;
[0040] FIG. 6 is a schematic illustration of a process with recycling for producing olefins and gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction into an isothermal Methanol-to-Olefin (MTO) reactor, utilizing scrubbed CO.sub.2 as a feed for MTO and converting ethylene into ethyl alcohol to increase Research Octane Number (RON) and Motor Octane Number (MON) of gasoline according to an embodiment of the present disclosure;
[0041] FIG. 7 is a schematic illustration of a process with recycling for producing olefins and gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction into an isothermal Methanol-to-Olefin (MTO) reactor and obtaining a C.sub.4 mix composition from a Depropanizer bottom fraction according to an embodiment of the present disclosure;
[0042] FIG. 8 is a schematic illustration of a process with complete recycling for producing olefins and gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction and C.sub.2 olefins into an isothermal Methanol-to-Olefin (MTO) reactor, utilizing scrubbed CO.sub.2 as a feed for Methanol-to-Olefin (MTO) reaction, utilizing a Demethanizer overhead vapor fraction as a feed for methanol synthesis according to an embodiment of the present disclosure;
[0043] FIG. 9 is a schematic illustration of a once-through process for producing olefins and gasoline from renewable sources comprising gasification of a Debutanizer bottom fraction and utilizing products of the gasification comprising hydrogen and CO.sub.2 as additional feed for producing methanol according to an embodiment of the present disclosure;
[0044] FIG. 10 is a schematic illustration of a process with recycling for producing olefins and gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction into an isothermal Methanol-to-Olefin (MTO) reactor, gasification of a Debutanizer bottom fraction, and utilizing products of the gasification comprising hydrogen and CO.sub.2 as additional feed for producing methanol according to an embodiment of the present disclosure; and
DETAILED DESCRIPTION OF EMBODIMENTS
[0045] The following detailed description illustrates embodiments of the present disclosure and ways in which they can be implemented. Although some modes of carrying out the present disclosure have been disclosed, those skilled in the art would recognize that other embodiments for carrying out or practicing the present disclosure are also possible.
[0046] According to a first aspect, the present disclosure provides a method for producing olefins and gasoline from renewable sources, the method comprising:
[0047] providing CO.sub.2 and hydrogen as feed to produce methanol in a methanol reactor, wherein the hydrogen is obtained from a water electrolyzer;
[0048] reacting the methanol in a Methanol-to-Olefin (MTO) reactor, preferably an isothermal MTO reactor, to produce a MTO reaction effluent comprising olefinic and non-olefinic hydrocarbons and water, wherein the water in the MTO reaction effluent is used at least partially as feed for the water electrolyzer, wherein non-converted CO.sub.2 from the methanol reactor is directed at least partially into the MTO reactor;
[0049] treating the MTO reaction effluent in a plurality of separation columns to separate the hydrocarbons, wherein the plurality of separation columns comprises a Deethanizer column, a Depropanizer column, a Debutanizer column, a C.sub.2 splitter column, and a C.sub.3 splitter column, wherein the separation of the hydrocarbons from the MTO reaction effluent comprises (i) separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons at the Deethanizer column, (ii) separating ethylene from the C.sub.2 hydrocarbons at the C.sub.2 splitter column, (iii) separating C.sub.3 hydrocarbons from C.sub.4+ hydrocarbons at the Depropanizer column, (iv) separating propylene from the C.sub.3 hydrocarbons at the C.sub.3 splitter column, and (v) separating C.sub.4 hydrocarbons as a Debutanizer overhead fraction at the Debutanizer column, wherein a fraction of the separated hydrocarbons settles at a bottom of the Debutanizer column as a Debutanizer bottom fraction after separation, wherein the Debutanizer bottom fraction comprises C.sub.5+ hydrocarbons;
[0050] hydrogenating at least a part of the Debutanizer bottom fraction with the hydrogen obtained from the water electrolyzer in a hydrogenation reactor to obtain a hydrogenated Debutanizer bottom fraction;
[0051] routing out at least a part of the hydrogenated Debutanizer bottom fraction as gasoline product, or
[0052] separating Liquefied Petroleum Gas (LPG) from the hydrogenated Debutanizer bottom fraction in a gasoline stabilizer column, routing out a LPG product as a gasoline stabilizer column overhead fraction, and routing out a stabilized gasoline product as a gasoline stabilizer column bottom fraction; and
[0053] routing out an olefin product, comprising propylene and optionally at least a part of the ethylene.
[0054] The method for producing the green olefins and the green gasoline from the renewable sources according to the present disclosure is of advantage in that the method enables the production of green olefins and green gasoline from clean/green educts that include H.sub.2 from electrolysis, and CO.sub.2 based MeOH synthesis. The method enables the production of the green olefins and the green gasoline from the renewable sources by utilizing feedstock such as H.sub.2, CO.sub.2 in a circular approach that enables better performances in different areas of the reaction path and huge flexibility of size and location combined with high-quality products. The method provides a smart way to convert and utilize CO.sub.2 to produce the green olefins as well as the green pump grade and sulfur-free gasoline.
[0055] A clean CO.sub.2 source is combined with hydrogen which is obtained by electrolyzing water in the water electrolyzer is directed into the methanol reactor for producing methanol. The clean CO.sub.2 source may enable the production of methanol and water in the methanol reactor in such proportion that no separation is required. The methanol produced in the methanol reactor is reacted in the isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. The water produced during the MTO reaction in the isothermal MTO reactor is used as feed for the water electrolyzer. The non-converted CO.sub.2 from the methanol reactor is directed into the isothermal MTO reactor that enables to lower partial pressure in the MTO reactor. The non-converted CO.sub.2 and the additional CO.sub.2 going into the MTO reactor increase propylene selectivity by lowering the partial pressure of reactants such as methanol and olefins. The amount of water entering the MTO reactor may be lowered to extend catalyst lifetime without losing propylene selectivity. The MTO reactor may preferably be designed to be operated isothermally, e. g. radial with plates or horizontal with plates. Optionally, the MTO reactor includes a salt bath and tubes for small applications.
[0056] The MTO reaction effluent is reacted in the plurality of separation columns to separate hydrocarbons, as defined in the independent claims of this disclosure.
[0057] Optionally, the separation of hydrocarbons in the plurality of separation columns includes
[0058] (i) treating the MTO reaction effluent in the Deethanizer column, wherein the Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene, and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons, and
[0059] (ii) treating the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons in the Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene, and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons, wherein the Depropanizer bottom fraction rich in C.sub.4+ hydrocarbons comprises 20-50% of C.sub.4 olefins and 50 to 80% of C.sub.4 paraffins, wherein the Depropanizer bottom fraction is at least partially directed to the hydrogenation reactor for hydrogenation.
[0060] A higher contribution comes from iso-butylene with 30 to 60% of all the C.sub.4 olefins in the stream and mostly iso-butane with over 60% of all the C.sub.4 paraffins in the stream.
[0061] Optionally, when the plurality of separation columns comprises a dehexanizer column, the separation of hydrocarbons in the plurality of separation columns comprises (i) treating the Debutanizer bottom fraction that is rich in C.sub.5+ hydrocarbons in the Dehexanizer column to produce a Dehexanizer overhead vapor fraction that is rich in hexane and hexene, and a Dehexanizer bottom fraction that is rich in C.sub.7+ hydrocarbons, wherein the Dehexanizer bottom fraction is directed to the hydrogenation reactor for hydrogenation.
[0062] The hydrogenation of Dehexanizer bottom fraction delivers a colorless product within specification margin on olefins and aromatics content.
[0063] Optionally, the C.sub.2 splitter column separates ethylene from ethane, the C.sub.3 splitter column separates propylene from propane, the ethylene and propylene are comprised in the overhead fractions of the C.sub.2 splitter column and the C.sub.3 splitter column, and the propane is directed at least partially to the hydrogenation reactor.
[0064] The C.sub.2 splitter and the C.sub.3 splitter are operated at high pressure, utilizing closed-cycle propylene, and ethylene refrigeration.
[0065] Optionally, at least a part of the ethylene is converted into ethanol and added to the gasoline product or stabilized gasoline product to increase the Research Octane Number (RON) and/or the Motor Octane Number (MON) of the gasoline.
[0066] The addition of the ethanol enables to stabilize the gasoline and the increase of the RON and MON of the gasoline improves ignition and combustion efficiency, thereby reducing pollution emissions.
[0067] Optionally, the method includes scrubbing the CO.sub.2 from the MTO reaction effluent using a CO.sub.2 scrubber to avoid the formation of solid CO.sub.2. At least a part of the scrubbed CO.sub.2 is provided as feed into the methanol reactor and the isothermal MTO reactor. Optionally, the CO.sub.2 scrubber is a chemical scrubber. The chemical CO.sub.2 scrubber uses caustic (NaOH solution) that can wash out bulk CO.sub.2 from the quenched MTO reaction effluent for recycling. Optionally, the CO.sub.2 scrubber is a physical scrubber. In an example, the physical scrubber is operated with methanol as washing agent, preferably methanol produced in the methanol reactor and optionally purified.
[0068] Optionally, the CO.sub.2 scrubber is arranged upstream of the plurality of separation columns. Optionally, the CO.sub.2 scrubber includes a CO.sub.2 adsorbent or a guard bed to remove final traces of CO.sub.2 before reacting the quenched MTO reaction effluent in the plurality of separation columns to separate hydrocarbons, as CO.sub.2 can form dry ice at cryogenic temperatures in the plurality of separation columns e.g., Demethanizer or Deethanizer and may block the equipment from functioning. The scrubbed CO.sub.2 is more preferably directed into the isothermal MTO reactor as the CO.sub.2 stream is probably not so pure.
[0069] Optionally, the CO.sub.2 scrubber is arranged downstream of the Deethanizer, as shown in the figures. However, arranging the CO.sub.2 scrubber upstream of the plurality of separation columns is generally preferred due to the reasons discussed above, and the skilled practitioner will interpret the figures so as to shift the CO.sub.2 scrubber to such upstream position.
[0070] Optionally, when the plurality of separation columns comprises a Demethanizer column, the method comprises directing the Deethanizer overhead vapor fraction into the Demethanizer column to produce an overhead fraction comprising methane.
[0071] Optionally, the method comprises directing at least a part of the overhead fraction from the Demethanizer column into the methanol reactor. The overhead fraction from the Demethanizer comprises methane, but also carbon monoxide, carbon dioxide, and hydrogen. Routing the overhead fraction from the Demethanizer column back into the methanol reactor increases the methanol yield. The methane comprised in the Demethanizer overhead fraction is an inret component in the methanol reactor and in the MTO reactor, and thus helps to reduce the methanol partial pressure in the MTO reactor which is increases the ethylene and propylene yield and also the catalyst lifetime.
[0072] Optionally, the method comprises recycling at least one element, selected from the following group:
[0073] (i) the Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons, (ii) the Debutanizer bottom fraction that is rich in C.sub.5+ hydrocarbons, (iii) the ethylene from the C.sub.2 splitter column overhead fraction,
(iv) the propane from the C.sub.3 splitter column overhead fraction,
[0074] at least partially into the MTO reactor. All of these elements can increase the ethylene and propylene yield, either by being converted to these light olefins, or by reducing the methanol partial pressure in the MTO reactor, or by a mixture of both effects.
[0075] Optionally, the method comprises quenching the MTO reaction effluent by treating the MTO reaction effluent with water before separating the MTO reaction effluent in the plurality of separation columns, wherein the water after quenching is directed at least partially into the water electrolyzer (122), optionally after water purification. The amount of fresh water supply is thus reduced.
[0076] Optionally, the CO.sub.2 used as the feed to produce methanol is free of sulfur components and amines therein. Both component groups may act as catalyst poisons either in the methanol reactor, or in the MTO reactor, or in both.
[0077] Optionally, the methanol produced in the methanol reactor is purified in a distillation column which is operated under a pressure ranging between 25 bar to 125 bar, and a temperature ranging between 200° C. and 350° C. The methanol may be produced using a single-stage reaction by directly reacting CO.sub.2 and H.sub.2. The methanol may be produced using a multi-stage reaction, where the CO.sub.2 first converted into CO through reverse water gas shift (RWGS). Inter-stage condensation and separation may be performed because an increase in carbon conversions may be achieved when methanol and water are condensed. Not all CO.sub.2 has to be converted for methanol production but most of the Hydrogen has to be converted in a once-through methanol reactor concept for producing green olefins and green gasoline without recycling. A part of the CO.sub.2 may be used as a diluting agent to replace the water in the isothermal Methanol-to-Olefin (MTO) reactor. The purge gas with CO.sub.2 and H.sub.2 may also be directed into the MTO the isothermal Methanol-to-Olefin (MTO) reactor. Optionally, the H.sub.2 is separated from CO.sub.2 before directing into the isothermal Methanol-to-Olefin (MTO) reactor.
[0078] Optionally, the methanol produced in the methanol reactor is a methanol-water mixture comprising in a range of 62 to 66 weight by percentage (wt-%) of methanol and about 34 to 38 weight by percentage (wt-%) of water. In an example, this methanol-water mixture may be fed into the MTO reactor without further separation, purification, or other treatment.
[0079] Optionally, the methanol-water mixture is reacted directly without any treatment in the MTO reactor. Hence, the requirement of DME Reactor where methanol vapor is partly converted to dimethyl ether (DME) is avoided.
[0080] Optionally, the methanol from the methanol reactor is separated from the water depending on an amount of CO.sub.2 available for the reaction to remove oxygenate in the MTO reactor. Optionally, the separated methanol is used as a fuel for Gas turbines. The percentage of separation of water depends on the amount of CO.sub.2 available for the reaction. Optionally, the CO.sub.2 used as a diluting agent. The amount of water used may be reduced accordingly to the amount of CO.sub.2 that may be sent to the isothermal MTO reactor. For example, if 20-30% of the CO.sub.2 is not converted, then 20-30% of the water may be removed. The removal of water corresponding to the amount of CO.sub.2 extends the lifetime of the catalyst in the isothermal MTO reactor and facilitates methanol synthesis at lower pressure in the methanol reactor as the conversion of all the CO.sub.2 is not required.
[0081] Optionally, the method comprises directing a purge gas with CO.sub.2 and H.sub.2 obtained from the methanol reactor into the isothermal MTO reactor. This is an alternative option to reduce the methanol partial pressure in the MTO reactor.
[0082] Optionally, the non-converted CO.sub.2 that is directed into the isothermal MTO reactor optimizes a partial pressure of reactants in the isothermal MTO reactor and increases a lifetime of a catalyst included in the isothermal MTO reactor. The non-converted CO.sub.2 may have a beneficial effect on carbon formation on the catalyst in the Methanol-to-Olefin (MTO) reactor. The non-converted CO.sub.2 inhibits the formation of coke in the Methanol-to-Olefin (MTO) reactor. The non-converted CO.sub.2 from the methanol synthesis with additional CO.sub.2 going into the MTO reactor allows better catalyst lifetime because of using less water than in the state of the art process.
[0083] Optionally, the CO.sub.2 is used as a diluting agent for the hydrogenation of the separated hydrocarbons. Adding diluting agents helps to limit the exothermicity of the hydrogenation reaction and avoids the formation of hot spots in the hydrogenation catalyst bed. The use of CO.sub.2 as diluting agent helps to save other inert gases like nitrogen.
[0084] Optionally, the CO.sub.2 and the hydrogen are used as diluting agents during oxidative regeneration of the catalyst in the isothermal MTO reactor. Optionally, Oxygen obtained by electrolyzing water in the water electrolyzer is used along with CO.sub.2 for regeneration. Hydrogen present in a minimal amount in the oxygen stream may be removed using membranes. The hydrogen molecule can dissociate into atoms on the surface of the membrane that is only permeable to hydrogen and then diffuse through the membrane lattice. Optionally, the membrane is a dense metal membrane that separates hydrogen with infinite selectivity.
[0085] Optionally, the method includes performing the MTO reaction in the MTO reactor (104), preferably in an isothermal MTO reactor (104), at a temperature in a range of 400 to 550° C., most preferably 420 to 480° C., and at a pressure in a range of 0.2 to 5 bara, most preferably 1 to 1.5 bara, to increase the C.sub.3 hydrocarbons yield in the MTO reaction effluent.
[0086] Optionally, the method includes using gasification of at least a part of hydrocarbon fractions, selected from the following group: [0087] Debutanizer bottom fraction, [0088] Depropanizer bottom fraction, [0089] C3 splitter column bottom fraction;
wherein products of the gasification comprising the hydrogen and the CO.sub.2 are used as feed for producing the methanol in the methanol reactor.
[0090] Optionally, the method includes obtaining CO.sub.2 from a biomass gasification utilizing oxygen from the water electrolyzer.
[0091] According to a second aspect, the present disclosure provides an apparatus for producing olefins and gasoline from renewable sources, the apparatus comprising:
[0092] a water electrolyzer (122);
[0093] a methanol reactor for producing methanol from CO.sub.2 and hydrogen, wherein the hydrogen is obtained from the water electrolyzer;
[0094] a Methanol-to-Olefin (MTO) reactor, preferably being designed to be operated isothermally, for reacting the methanol to produce an MTO reaction effluent, wherein water produced during an MTO reaction in the Methanol-to-Olefin (MTO) reactor is used as feed for the water electrolyzer, wherein non-converted CO.sub.2 from the methanol reactor is directed at least partially into the MTO reactor;
[0095] a plurality of separation columns for treating the MTO reaction effluent to separate hydrocarbons, wherein the plurality of separation columns comprises a Deethanizer column, a Depropanizer column, a Debutanizer column, a C.sub.2 splitter column, and a C.sub.3 splitter column, wherein the plurality of separation columns is configured to: [0096] (i) separate C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons at the Deethanizer column, [0097] (ii) separate ethylene from the C.sub.2 hydrocarbons at the C.sub.2 splitter column, [0098] (iii) separate C.sub.3 hydrocarbons from C.sub.4+ hydrocarbons at the Depropanizer column, [0099] (iv) separate propylene from the C.sub.3 hydrocarbons at the C.sub.3 splitter column, and [0100] (v) separate C.sub.4 hydrocarbons as a Debutanizer overhead fraction at the Debutanizer column, wherein a fraction of the separated hydrocarbons settles at a bottom of the Debutanizer column as a Debutanizer bottom fraction after separation, wherein the Debutanizer bottom fraction comprises C.sub.5+ hydrocarbons;
[0101] a hydrogenation reactor for hydrogenating at least a part of the Debutanizer bottom fraction with the hydrogen obtained from the water electrolyzer to obtain a hydrogenated Debutanizer bottom fraction;
[0102] optionally a gasoline stabilizer column for stabilizing the hydrogenated Debutanizer bottom fraction to produce a gasoline product and a Liquefied Petroleum Gas (LPG) product.
[0103] The apparatus for producing the green light olefins and the green pump grade gasoline using CO.sub.2 and hydrogen from the renewable sources according to present disclosure enables the production of the green light olefins and the green pump grade gasoline from clean/green educts that include H.sub.2 from electrolysis, and CO.sub.2 based MeOH synthesis. The apparatus enables utilizing feedstock such as H.sub.2, CO.sub.2 in a circular approach that enables better performances in the different areas of the reaction path and huge flexibility of size and location combined with high-quality products. The apparatus for producing the green olefins and the green gasoline from the renewable sources can be fully optimized for smaller capacities for local production and integration into other processes and fluctuating operation conditions.
[0104] Embodiments of the present disclosure substantially eliminate or at least partially address the aforementioned technical drawbacks in existing technologies in providing a system and method for producing green light olefins and green pump grade utilizing H.sub.2 and CO.sub.2 from renewable resources.
Detailed Description of the Drawings
[0105] FIG. 1 is a schematic illustration of an apparatus 100 for producing green olefins and green gasoline from renewable sources according to an embodiment of the present disclosure. The apparatus 100 includes a methanol reactor 102, an isothermal Methanol-to-Olefin (MTO) reactor 104, a plurality of separation columns comprising a Deethanizer column 106, a Depropanizer column 108, and a Debutanizer column 110, a hydrogenation chamber 112, a gasoline stabilizer 114, a C.sub.2 splitter column 116, a C.sub.3 splitter column 117 (shown together with 116 as one block for simplification, but 117 representing a separate separation column), and a water electrolyzer 122. For the purposes of this disclosure, the separation columns are to be understood as performing the separation by distillation or rectification, unless otherwise specified. The methanol reactor 102 produces methanol from CO.sub.2 and hydrogen. The CO.sub.2 is obtained from a CO.sub.2 feed chamber 118 and the hydrogen is obtained from a hydrogen feed chamber 120. The hydrogen is produced by electrolyzing water in the water electrolyzer 122. The isothermal Methanol-to-Olefin (MTO) reactor 104 reacts the methanol produced in the methanol reactor 102 to produce an MTO reaction effluent. The water produced during MTO reaction in the isothermal Methanol-to-Olefin (MTO) reactor 104 is used as feed for the water electrolyzer 122. Non-converted CO.sub.2 from the methanol reactor 102 is directed into the isothermal Methanol-to-Olefin (MTO) reactor 104. The Deethanizer column 106, the Depropanizer column 108, and the Debutanizer column 110 treats the MTO reaction effluent produced in the isothermal Methanol-to-Olefin (MTO) reactor 104 to separate hydrocarbons from the MTO reaction effluent. The Deethanizer column 106 separates C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Depropanizer column 108 separates C.sub.3 hydrocarbons from C.sub.4+ hydrocarbons. The Debutanizer column 110 separates C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons. A fraction of the separated hydrocarbons comprising C.sub.5+ hydrocarbons settles at a bottom of the Debutanizer column 110 after separation. The hydrogenation reactor 112 hydrogenates the fraction of separated hydrocarbons settled at the bottom of the Debutanizer column 110 with the hydrogen obtained from the water electrolyzer 122. The gasoline stabilizer column 114 stabilizes hydrogenated hydrocarbons from the hydrogenation reactor 112 to produce the green gasoline as bottom fraction and Liquefied Petroleum Gas (LPG) as overhead fraction. The C.sub.2 splitter column 116 and C.sub.3 splitter column 117 produces ethylene and propylene as the green olefins by splitting the remaining separated hydrocarbons from the plurality of separation columns comprising the Deethanizer column 106, the Depropanizer column 108, and the Debutanizer column 110. Ethylene and propylene are recovered as overhead fractions of the respective splitter columns 116 and 117.
[0106] FIG. 2 is a schematic illustration of a once-through process 200 for producing green olefins and green gasoline from renewable sources utilizing scrubbed CO.sub.2 as a feed for producing methanol and Methanol-to-Olefin (MTO) reaction according to an embodiment of the present disclosure. At a step 202, CO.sub.2 is obtained from a CO.sub.2 feed chamber. At a step 204, hydrogen is obtained from a hydrogen feed chamber. The hydrogen is produced by electrolyzing water in a water electrolyzer 212 and supplied to the hydrogen feed chamber 204 (not shown). At a step 206, methanol is produced in a methanol reactor by utilizing the CO.sub.2 obtained from the CO.sub.2 feed chamber and the Hydrogen obtained from the hydrogen feed chamber. At a step 208, the methanol is reacted in an isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. Non-converted CO.sub.2 from the methanol reactor is directed into the isothermal Methanol-to-Olefin reactor (MTO) 208. Optionally, a part of the CO.sub.2 obtained from the CO.sub.2 feed chamber is directed into the isothermal Methanol-to-Olefin (MTO) reactor 208 as diluting agent for the MTO reaction. At a step 210, the MTO reaction effluent is quenched by treating the MTO reaction effluent with water in a quenching chamber. At a step 212, the quenched water is supplied as a feed to the water electrolyzer. At a step 214, the CO.sub.2 from the quenched MTO reaction effluent is scrubbed using a CO.sub.2 scrubber. The scrubbed CO.sub.2 is directed into the CO.sub.2 feed chamber. At a step 216, the MTO reaction effluent is reacted in a Deethanizer column for separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons. At a step 218, the Deethanizer overhead vapor fraction is reacted in a Demethanizer column for separating C.sub.1 hydrocarbons from C.sub.2+ hydrocarbons. The Demethanizer column produces a Demethanizer overhead vapor fraction rich in CH.sub.4, CO.sub.2, H.sub.2, and CO and a Demethanizer bottom fraction that is rich in C.sub.2+ hydrocarbons comprising olefins and paraffins. The Demethanizer overhead vapor fraction that is rich in methane is used as fuel gas and/or can be recycled at least partially to the methanol reactor. At a step 220, C.sub.2 olefins are separated from C.sub.2 paraffins in a C.sub.2 splitter column. The C.sub.2 paraffins from the C.sub.2 splitter are used as fuel gas. At a step 222, the quenched MTO reaction effluent is reacted in a Debutanizer column for separating C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons. A fraction of separated hydrocarbons comprising C.sub.5+ hydrocarbons settles at a bottom of the Debutanizer column after the reaction. At a step 224, the fraction of separated hydrocarbons in the Debutanizer column is hydrogenated with the hydrogen from the hydrogen feed chamber. The fraction of separated hydrocarbons from the Debutanizer column comprises C.sub.5+ hydrocarbons. At a step 226, the hydrogenated hydrocarbons are stabilized in a gasoline stabilizer column to produce green gasoline as bottom product and Liquefied Petroleum Gas (LPG) as overhead product. At a step 228, the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons and a Debutanizer overhead vapor fraction rich in butane and butylene are treated in a Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons. The Depropanizer bottom fraction is directed into a hydrogenation reactor for hydrogenation. At a step 230, the propylene is separated from the propane in the Depropanizer overhead vapor fraction in a C.sub.3 splitter. The propane from the C.sub.3 splitter is directed along with the fraction of separated hydrocarbons from the Debutanizer column into the hydrogenation reactor for hydrogenation.
[0107] FIG. 3 is a schematic illustration of a once-through process 300 for producing green olefins and green gasoline from renewable sources utilizing scrubbed CO.sub.2 as a feed for Methanol-to-Olefin (MTO) reaction according to an embodiment of the present disclosure. At a step 302, CO.sub.2 is obtained from a CO.sub.2 feed chamber. At a step 304, hydrogen is obtained from a hydrogen feed chamber. The hydrogen is produced by electrolyzing water in a water electrolyzer 312 and supplied to the hydrogen feed chamber 304 (not shown). *** At a step 306, methanol is produced in a methanol reactor by utilizing the CO.sub.2 obtained from the CO.sub.2 feed chamber and the Hydrogen obtained from the hydrogen feed chamber. At a step 308, the methanol is reacted in an isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. The non-converted CO.sub.2 from the methanol reactor is directed into the isothermal Methanol-to-Olefin (MTO) reactor. At a step 310, the MTO reaction effluent is quenched by treating the MTO reaction effluent with water in a quenching chamber. At a step 312, the quenched water is supplied as a feed to the water electrolyzer. At a step 314, the CO.sub.2 from the MTO reaction effluent is scrubbed using a CO.sub.2 scrubber. The scrubbed CO.sub.2 is directed into the isothermal Methanol-to-Olefin (MTO) reactor along with the CO.sub.2 from the CO.sub.2 feed chamber for the MTO reaction. At a step 316, the quenched MTO reaction effluent is reacted in a Deethanizer column for separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons. At a step 318, the Deethanizer overhead vapor fraction is treated in a Demethanizer column for separating C.sub.1 hydrocarbons from C.sub.2+ hydrocarbons. The Demethanizer column produces a Demethanizer overhead vapor fraction rich in CH.sub.4, CO.sub.2, H.sub.2, and CO and a Demethanizer bottom fraction that is rich in C.sub.2+ hydrocarbons comprising olefins and paraffins. The overhead vapor fraction that is rich in methane is used as fuel gas. At a step 320, C.sub.2 olefins are separated from C.sub.2 paraffins in a C.sub.2 splitter column. The C.sub.2 paraffins from the C.sub.2 splitter column are used as fuel gas. At a step 322, the quenched MTO reaction effluent is reacted in a Debutanizer column for separating C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons. A fraction of separated hydrocarbons comprising C.sub.5+ hydrocarbons settles at a bottom of the Debutanizer column after the reaction. At a step 324, the fraction of separated hydrocarbons in the Debutanizer column is hydrogenated with the hydrogen from the hydrogen feed chamber. At a step 326, the hydrogenated hydrocarbons are stabilized in a gasoline stabilizer column to produce green gasoline and Liquefied Petroleum Gas (LPG). At a step 328, the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons and a Debutanizer overhead vapor fraction rich in butane and butylene are treated in a Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons. The Depropanizer bottom fraction is directed into the hydrogenation reactor for hydrogenation. At a step 330, the propylene is separated from the propane in the Depropanizer overhead vapor fraction in a C.sub.3 splitter column. The propane from the C.sub.3 splitter column is directed along with the fraction of separated hydrocarbons from the Debutanizer column into the hydrogenation reactor for hydrogenation.
[0108] FIG. 4 is a schematic illustration of a once-through process 400 for producing green olefins and green gasoline from renewable sources comprising converting green ethylene into ethyl alcohol to increase Research Octane Number (RON) and Motor Octane Number (MON) of green gasoline according to an embodiment of the present disclosure. At a step 402, CO.sub.2 is obtained from a CO.sub.2 feed chamber. At a step 404, hydrogen is obtained from a hydrogen feed chamber. The hydrogen is produced by electrolyzing water in a water electrolyzer 412 and supplied to the hydrogen feed chamber 404 (not shown). At a step 406, methanol is produced in a methanol reactor utilizing the CO.sub.2 obtained from the CO.sub.2 feed chamber and the Hydrogen obtained from the hydrogen feed chamber. At a step 408, the methanol is reacted in an isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. The non-converted CO.sub.2 from the methanol reactor is directed into the isothermal Methanol-to-Olefin (MTO) reactor. At a step 410, the MTO reaction effluent is quenched by treating the MTO reaction effluent with water in a quenching chamber. At a step 412, the quenched water is supplied as a feed to the water electrolyzer. At a step 414, CO.sub.2 from the MTO reaction effluent is scrubbed using a CO.sub.2 scrubber. The scrubbed CO.sub.2 is directed into the isothermal MTO reactor along with the CO.sub.2 from the CO.sub.2 feed chamber for the MTO reaction. At a step 416, the quenched MTO reaction effluent is treated in a Deethanizer column for separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons. At a step 418, the Deethanizer overhead vapor fraction is treated in a Demethanizer column for separating C.sub.1 hydrocarbons from C.sub.2+ hydrocarbons. The Demethanizer column produces a Demethanizer overhead vapor fraction rich in CH.sub.4, CO.sub.2, H.sub.2, and CO and a Demethanizer bottom fraction that is rich in C.sub.2+ hydrocarbons comprising olefins and paraffins. The overhead vapor fraction that is rich in methane is used as fuel gas. At a step 420, C.sub.2 olefins are separated from C.sub.2 paraffins in a C.sub.2 splitter column. The C.sub.2 paraffins from the C.sub.2 splitter column are used as fuel gas. The C.sub.2 olefins are hydrated with water to produce ethanol. At a step 422, the quenched MTO reaction effluent is treated in a Debutanizer column for separating C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons at the Debutanizer column. A fraction of the separated hydrocarbons comprising C.sub.5+ hydrocarbons settles at a bottom of the Debutanizer column after separation. At a step 424, the fraction of separated hydrocarbons in the Debutanizer column is hydrogenated with the hydrogen from the hydrogen feed chamber. At a step 426, the hydrogenated hydrocarbons are stabilized in a gasoline stabilizer column to produce green gasoline and Liquefied Petroleum Gas (LPG). The ethanol is used to increase the Research Octane Number (RON) and Motor Octane Number (MON) of the green gasoline. At a step 428, the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons and a Debutanizer overhead vapor fraction rich in butane and butylene are treated in a Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons. The Depropanizer bottom fraction is directed into the hydrogenation reactor for hydrogenation. At a step 430, the propylene is separated from the propane in the Depropanizer overhead vapor fraction in a C.sub.3 splitter column. The propane from the C.sub.3 splitter column is directed along with the fraction of separated hydrocarbons from the Debutanizer column into the hydrogenation reactor for hydrogenation.
[0109] FIG. 5 is a schematic illustration of a process 500 with recycling for producing green olefins and green gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction into an isothermal Methanol-to-Olefin (MTO) reactor and utilizing scrubbed CO.sub.2 as a feed for Methanol-to-Olefin (MTO) reaction according to an embodiment of the present disclosure. At a step 502, CO.sub.2 is obtained from a CO.sub.2 feed chamber. At a step 504, hydrogen is obtained from a hydrogen feed chamber. The hydrogen is produced by electrolyzing water in a water electrolyzer 512 and supplied to the hydrogen feed chamber 504 (not shown). At a step 506, methanol is produced in a methanol reactor utilizing the CO.sub.2 obtained from the CO.sub.2 feed chamber and the Hydrogen obtained from the hydrogen feed chamber. At a step 508, the methanol is reacted in an isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. The non-converted CO.sub.2 from the methanol reactor is directed into the isothermal Methanol-to-Olefin (MTO) reactor. At a step 510, the MTO reaction effluent is quenched by treating the MTO reaction effluent with water in a quenching chamber. At a step 512, the quenched water is supplied as a feed to the water electrolyzer. At a step 514, CO.sub.2 from the MTO reaction effluent is scrubbed using a CO.sub.2 scrubber. The scrubbed CO.sub.2 is directed into the isothermal Methanol-to-Olefin (MTO) reactor along with the CO.sub.2 from the CO.sub.2 feed chamber for the MTO reaction. At a step 516, the quenched MTO reaction effluent is treated in a Deethanizer column for separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons. At a step 518, the Deethanizer overhead vapor fraction is treated in a Demethanizer column for separating C.sub.1 hydrocarbons from C.sub.2+ hydrocarbons. The Demethanizer column produces a Demethanizer overhead vapor fraction rich in CH.sub.4, CO.sub.2, H.sub.2, and CO and a Demethanizer bottom fraction that is rich in C.sub.2+ hydrocarbons comprising olefins and paraffins. The overhead vapor fraction that is rich in methane is used as fuel gas. At a step 520, C.sub.2 olefins are separated from C.sub.2 paraffins in a C.sub.2 splitter column. The C.sub.2 paraffins from the C.sub.2 splitter column are used as fuel gas. At a step 522, the quenched MTO reaction effluent is treated in a Debutanizer column for separating C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons at the Debutanizer column. A fraction of separated hydrocarbons comprising C.sub.5+ hydrocarbons settles at a bottom of the Debutanizer column after the reaction. A first fraction of the separated hydrocarbons is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. At a step 524, remaining fraction of the separated hydrocarbons in the Debutanizer column is hydrogenated with the hydrogen from the hydrogen feed chamber. At a step 526, the hydrogenated hydrocarbons are stabilized in a gasoline stabilizer column to produce green gasoline and Liquefied Petroleum Gas (LPG). At a step 528, the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons and a Debutanizer overhead vapor fraction rich in butane and butylene are treated in a Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons. A portion of the Depropanizer bottom fraction is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. The remaining portion of the Depropanizer bottom fraction is directed to the hydrogenation reactor for hydrogenation. At a step 530, the propylene is separated from propane in the Depropanizer overhead vapor fraction in a C.sub.3 splitter column. The propane from the C.sub.3 splitter is directed along with the remaining fraction of separated hydrocarbons from the Debutanizer column into the hydrogenation reactor for hydrogenation.
[0110] FIG. 6 is a schematic illustration of a process 600 with recycling for producing green olefins and green gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction into an isothermal Methanol-to-Olefin (MTO) reactor, utilizing scrubbed CO.sub.2 as a feed for MTO and converting green ethylene into ethyl alcohol to increase Research Octane Number (RON) and Motor Octane Number (MON) of green gasoline according to an embodiment of the present disclosure. At a step 602, CO.sub.2 is obtained from a CO.sub.2 feed chamber. At a step 604, hydrogen is obtained from a hydrogen feed chamber. The hydrogen is produced by electrolyzing water in a water electrolyzer 612 and supplied to the hydrogen feed chamber 604 (not shown). At a step 606, methanol is produced in a methanol reactor utilizing the CO.sub.2 obtained from the CO.sub.2 feed chamber and the Hydrogen obtained from the hydrogen feed chamber. At a step 608, the methanol is reacted in an isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. The non-converted CO.sub.2 from the methanol reactor is directed into the isothermal Methanol-to-Olefin (MTO) reactor. At a step 610, the MTO reaction effluent is quenched by treating the MTO reaction effluent with water in a quenching chamber. At a step 612, the quenched water is supplied as a feed to the water electrolyzer. At a step 614, CO.sub.2 from the MTO reaction effluent is scrubbed using a CO.sub.2 scrubber. The scrubbed CO.sub.2 is directed into the isothermal Methanol-to-Olefin (MTO) reactor along with the CO.sub.2 from the CO.sub.2 feed chamber for the MTO reaction. At a step 616, the quenched MTO reaction effluent is treated in a Deethanizer column for separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons. At a step 618, the Deethanizer overhead vapor fraction is treated in a Demethanizer column for separating C.sub.1 hydrocarbons from C.sub.2+ hydrocarbons. The Demethanizer column produces a Demethanizer overhead vapor fraction rich in CH.sub.4, CO.sub.2, H.sub.2, and CO and a Demethanizer bottom fraction that is rich in C.sub.2+ hydrocarbons comprising olefins and paraffins. The overhead vapor fraction that is rich in methane is used as fuel gas. At a step 620, C.sub.2 olefins are separated from C.sub.2 paraffins in a C.sub.2 splitter column. The C.sub.2 paraffins from the C.sub.2 splitter column are used as fuel gas. The C.sub.2 olefins are hydrated with water to produce ethanol. At a step 622, the quenched MTO reaction effluent is treated in a Debutanizer column for separating C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons at the Debutanizer column. A fraction of separated hydrocarbons comprising C.sub.5+ hydrocarbons settles at a bottom of the Debutanizer column after the reaction. A first fraction of the separated hydrocarbons is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. At a step 624, the remaining fraction of separated hydrocarbons in the Debutanizer column is hydrogenated with the hydrogen from the hydrogen feed chamber. At a step 626, the hydrogenated hydrocarbons are stabilized in a gasoline stabilizer column to produce green gasoline and Liquefied Petroleum Gas (LPG). The ethanol produced by hydrating C.sub.2 olefins from the C.sub.2 splitter is used to increase the Research Octane Number (RON) and Motor Octane Number (MON) of the green gasoline. At a step 628, the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons and a Debutanizer overhead vapor fraction rich in butane and butylene are treated in a Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons. A first portion of the Depropanizer bottom fraction is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction and the remaining portion of the Depropanizer bottom fraction is directed into the hydrogenation reactor for hydrogenation. At a step 630, the propylene is separated from propane in the Depropanizer overhead vapor fraction in a C.sub.3 splitter column. The propane from the C.sub.3 splitter column is directed along with the remaining fraction of separated hydrocarbons from the Debutanizer column into the hydrogenation reactor for hydrogenation.
[0111] FIG. 7 is a schematic illustration of a process 700 with recycling for producing green olefins and green gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction into an isothermal Methanol-to-Olefin (MTO) reactor and obtaining a C.sub.4 mix composition from a Depropanizer bottom fraction according to an embodiment of the present disclosure. At a step 702, CO.sub.2 is obtained from a CO.sub.2 feed chamber. At a step 704, hydrogen is obtained from a hydrogen feed chamber. The hydrogen is produced by electrolyzing water in a water electrolyzer 712 and supplied to the hydrogen feed chamber 704 (not shown). At a step 706, methanol is produced in a methanol reactor utilizing the CO.sub.2 obtained from the CO.sub.2 feed chamber and the Hydrogen obtained from the hydrogen feed chamber. At a step 708, the methanol is reacted in an isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. The non-converted CO.sub.2 from the methanol reactor is directed into the isothermal Methanol-to-Olefin (MTO) reactor. At a step 710, the MTO reaction effluent is quenched by treating the MTO reaction effluent with water in a quenching chamber. At a step 712, the quenched water is supplied as a feed to the water electrolyzer. At a step 714, CO.sub.2 from the MTO reaction effluent is scrubbed using a CO.sub.2 scrubber. The scrubbed CO.sub.2 is directed into the isothermal MTO reactor along with the CO.sub.2 from the CO.sub.2 feed chamber for the MTO reaction. At a step 716, the quenched MTO reaction effluent is treated in a Deethanizer column for separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons. The Deethanizer overhead vapor fraction is used as fuel gas. At a step 718, the quenched MTO reaction effluent is treated in a Debutanizer column for separating C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons. A fraction of the separated hydrocarbons comprising C.sub.5+ hydrocarbons settles at a bottom of the Debutanizer column after separation. A portion of the separated hydrocarbons is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. At a step 720, the remaining portion of separated hydrocarbons in the Debutanizer column is hydrogenated with the hydrogen from the hydrogen feed chamber to produce green gasoline. At a step 722, the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons and a Debutanizer overhead vapor fraction rich in butane and butylene are treated in a Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons. The Depropanizer bottom fraction may also have a considerable amount of aromatic hydrocarbons. A portion of the Depropanizer bottom fraction is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. The remaining portion of the Depropanizer bottom fraction is obtained as a C.sub.4 mix composition comprising 20-50% C.sub.4 olefins and 50 to 80% C.sub.4 paraffins. Higher contribution for C.sub.4 olefins comes from iso-butylene with 30 to 60% of all the C.sub.4 olefins in the stream and for C.sub.4 paraffins, mostly iso-butane with over 60% of all the C.sub.4 paraffins in the stream. At a step 724, the propylene is separated from propane in the Depropanizer overhead vapor fraction in a C.sub.3 splitter column. The propane from the C.sub.3 splitter column is directed along with the remaining fraction of separated hydrocarbons from the Debutanizer column into the hydrogenation reactor for hydrogenation.
[0112] FIG. 8 is a schematic illustration of a process 800 with complete recycle for producing green olefins and green gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction and C.sub.2 olefins into an isothermal Methanol-to-Olefin (MTO) reactor, utilizing scrubbed CO.sub.2 as a feed for MTO (Methanol-to-Olefin) reaction, utilizing a Demethanizer overhead vapor fraction as a feed for methanol synthesis according to an embodiment of the present disclosure. At a step 802, CO.sub.2 is obtained from a CO.sub.2 feed chamber. At a step 804, hydrogen is obtained from a hydrogen feed chamber. The hydrogen is produced by electrolyzing water in a water electrolyzer 812 and supplied to the hydrogen feed chamber 804 (not shown). At a step 806, methanol is produced in a methanol reactor utilizing the CO.sub.2 obtained from the CO.sub.2 feed chamber and the Hydrogen obtained from the hydrogen feed chamber. At a step 808, the methanol is reacted in an isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. The non-converted CO.sub.2 from the methanol reactor is directed into the isothermal MTO reactor. At a step 810, the MTO reaction effluent is quenched by treating the MTO reaction effluent with water in a quenching chamber. At a step 812, the quenched water is supplied as a feed to the water electrolyzer. At a step 814, CO.sub.2 from the MTO reaction effluent is scrubbed using a CO.sub.2 scrubber. The scrubbed CO.sub.2 is directed into the isothermal MTO reactor along with the CO.sub.2 from the CO.sub.2 feed chamber for the MTO reaction. At a step 816, the quenched MTO reaction effluent is treated in a Deethanizer column for separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons. At a step 818, the Deethanizer overhead vapor fraction is treated in a Demethanizer column for separating C.sub.1 hydrocarbons from C.sub.2+ hydrocarbons. The Demethanizer column produces a Demethanizer overhead vapor fraction rich in CH.sub.4, CO.sub.2, H.sub.2, and CO and a Demethanizer bottom fraction that is rich in C.sub.2+ hydrocarbons comprising olefins and paraffins. A portion of the Demethanizer overhead vapor fraction is directed as a feed for producing methanol into the methanol reactor. The portion of the Demethanizer overhead vapor fraction that is rich in methane is used as fuel gas. At a step 820, C.sub.2 olefins are separated from C.sub.2 paraffins in a C.sub.2 splitter column. The C.sub.2 paraffins from the C.sub.2 splitter column are used as fuel gas. The separated C.sub.2 olefins from the C.sub.2 splitter is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. At a step 822, the quenched MTO reaction effluent is teated in a Debutanizer column for separating C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons at the Debutanizer column. A fraction of the separated hydrocarbons settles at a bottom of the Debutanizer column after separation. A portion of the separated hydrocarbons is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. At a step 824, the remaining portion of separated hydrocarbons in the Debutanizer column is hydrogenated with the hydrogen from the hydrogen feed chamber. The fraction of separated hydrocarbons from the Debutanizer column comprises C.sub.5+ hydrocarbons. At a step 826, the hydrogenated hydrocarbons are stabilized in a gasoline stabilizer column to produce green gasoline and Liquefied Petroleum Gas (LPG). At a step 828, the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons and a Debutanizer overhead vapor fraction rich in butane and butylene are treated in a Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons. The Depropanizer bottom fraction may also have a considerable amount of C.sub.5 to C.sub.9 hydrocarbons (olefins+paraffins) and aromatic hydrocarbons. A portion of the Depropanizer bottom fraction is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. Remaining portion of the Depropanizer bottom fraction is directed to the hydrogenation reactor for hydrogenation. At a step 830, the propylene is separated from propane in the Depropanizer overhead vapor fraction in a C.sub.3 splitter column. The propane from the C.sub.3 splitter column is directed along with the remaining fraction of separated hydrocarbons from the Debutanizer column into the hydrogenation reactor for hydrogenation.
[0113] FIG. 9 is a schematic illustration of a once-through process 900 for producing green olefins and green gasoline from renewable sources comprising gasification of a Debutanizer bottom fraction and utilizing products of the gasification comprising hydrogen and CO.sub.2 as additional feed for producing methanol according to an embodiment of the present disclosure. At a step 902, CO.sub.2 is obtained from a CO.sub.2 feed chamber. At a step 904, hydrogen is obtained from a hydrogen feed chamber. The hydrogen is produced by electrolyzing water in a water electrolyzer 912 and supplied to the hydrogen feed chamber 904 (not shown). At a step 906, methanol is produced in a methanol reactor utilizing the CO.sub.2 obtained from the CO.sub.2 feed chamber and the Hydrogen obtained from the hydrogen feed chamber. At a step 908, the methanol is reacted in an isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. The non-converted CO.sub.2 from the methanol reactor is directed into the isothermal Methanol-to-Olefin (MTO) reactor. At a step 910, the MTO reaction effluent is quenched by treating the MTO reaction effluent with water in a quenching chamber. At a step 912, the quenched water is supplied as a feed to the water electrolyzer. At a step 914, CO.sub.2 from the MTO reaction effluent is scrubbed using a CO.sub.2 scrubber. The scrubbed CO.sub.2 is directed into the isothermal Methanol-to-Olefin (MTO) reactor along with the CO.sub.2 from the CO.sub.2 feed chamber for the MTO reaction. At a step 916, the quenched MTO reaction effluent is treated in a Deethanizer column for separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons. At a step 918, the Deethanizer overhead vapor fraction is treated in a Demethanizer column for separating C.sub.1 hydrocarbons from C.sub.2+ hydrocarbons. The Demethanizer column produces a Demethanizer overhead vapor fraction rich in CH.sub.4, CO.sub.2, H.sub.2, and CO and a Demethanizer bottom fraction that is rich in C.sub.2+ hydrocarbons comprising olefins and paraffins. A portion of the Demethanizer overhead vapor fraction is directed into the methanol reactor for methanol synthesis. The remaining portion of Demethanizer overhead vapor fraction that is rich in methane is used as fuel gas. At a step 920, C.sub.2 olefins are separated from C.sub.2 paraffins in a C.sub.2 splitter column. The C.sub.2 olefins are directed into the isothermal Methanol-to-Olefin (MTO) reactor and used as a feed for MTO (Methanol-to-Olefin) reaction. The C.sub.2 paraffins from the C.sub.2 splitter column are used as fuel gas. At a step 922, the quenched MTO reaction effluent is treated in a Debutanizer column for separating C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons at the Debutanizer column. A fraction of the separated hydrocarbons comprising C.sub.5+ hydrocarbons settles at a bottom of the Debutanizer column after separation. At a step 924, the separated hydrocarbons comprising the C.sub.5+ hydrocarbons in the Debutanizer column are subjected to gasification in a gasification reactor. The products of the gasification comprise hydrogen and CO.sub.2. The hydrogen is directed into the hydrogen feed chamber and the CO.sub.2 is directed into the CO.sub.2 feed chamber. The products of the gasification comprising hydrogen and CO.sub.2 are used as additional feed for producing the methanol in the methanol reactor. At a step 926, the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons and a Debutanizer overhead vapor fraction rich in butane and butylene are treated in a Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons. The Depropanizer bottom fraction may also have a considerable amount of C.sub.5 to C.sub.9 hydrocarbons (olefins+paraffins) and aromatic hydrocarbons. A portion of the Depropanizer bottom fraction is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. Remaining portion of the Depropanizer bottom fraction is directed to the hydrogenation reactor for hydrogenation. At a step 928, the propylene is separated from propane in the Depropanizer overhead vapor fraction in a C.sub.3 splitter column. The propane from the C.sub.3 splitter column is directed along with the fraction of separated hydrocarbons from the Debutanizer column in the gasification reactor for gasification.
[0114] FIG. 10 is a schematic illustration of a process 1000 with recycling for producing green olefins and green gasoline from renewable sources comprising directing a portion of a Debutanizer and a Depropanizer bottom fraction into an isothermal Methanol-to-Olefin (MTO) reactor, gasification of a Debutanizer bottom fraction, and utilizing products of the gasification comprising hydrogen and CO.sub.2 as additional feed for producing methanol according to an embodiment of the present disclosure. At a step 1002, CO.sub.2 is obtained from a CO.sub.2 feed chamber. At a step 1004, hydrogen is obtained from a hydrogen feed chamber. The hydrogen is produced by electrolyzing water in a water electrolyzer 1012 and supplied to the hydrogen feed chamber 1004 (not shown). At a step 1006, methanol is produced in a methanol reactor utilizing the CO.sub.2 obtained from the CO.sub.2 feed chamber and the Hydrogen obtained from the hydrogen feed chamber. At a step 1008, the methanol is reacted in an isothermal Methanol-to-Olefin (MTO) reactor to produce an MTO reaction effluent. The non-converted CO.sub.2 from the methanol reactor is directed into the isothermal Methanol-to-Olefin (MTO) reactor. At a step 1010, the MTO reaction effluent is quenched by treating the MTO reaction effluent with water in a quenching chamber. At a step 1012, the quenched water is supplied as a feed to the water electrolyzer. At a step 1014, CO.sub.2 from the MTO reaction effluent is scrubbed using a CO.sub.2 scrubber. The scrubbed CO.sub.2 is directed into the isothermal Methanol-to-Olefin (MTO) reactor along with the CO.sub.2 from the CO.sub.2 feed chamber for the MTO reaction. At a step 1016, the quenched MTO reaction effluent is treated in a Deethanizer column for separating C.sub.2 hydrocarbons from C.sub.3+ hydrocarbons. The Deethanizer column produces a Deethanizer overhead vapor fraction that is rich in ethane and ethylene and a Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons. At a step 1018, the Deethanizer overhead vapor fraction is treated in a Demethanizer column for separating C.sub.1 hydrocarbons from C.sub.2+ hydrocarbons. The Demethanizer column produces a Demethanizer overhead vapor fraction rich in CH.sub.4, CO.sub.2, H.sub.2, and CO and a Demethanizer bottom fraction that is rich in C.sub.2+ hydrocarbons comprising olefins and paraffins. A portion of the Demethanizer overhead vapor fraction is directed into the methanol reactor for methanol synthesis. Remaining portion of the Demethanizer overhead vapor fraction that is rich in methane is used as fuel gas. At a step 1020, C.sub.2 olefins are separated from C.sub.2 paraffins in a C.sub.2 splitter column. The C.sub.2 olefins are directed into the isothermal Methanol-to-Olefin (MTO) reactor and used as a feed for MTO (Methanol-to-Olefin) reaction. The C.sub.2 paraffins from the C.sub.2 splitter column are used as fuel gas. At a step 1022, the quenched MTO reaction effluent is treated in a Debutanizer column for separating C.sub.4 hydrocarbons from C.sub.5+ hydrocarbons at the Debutanizer column. A fraction of the separated hydrocarbons settles at a bottom of the Debutanizer column after separation. At a step 1024, the separated hydrocarbons comprising C.sub.5+ hydrocarbons in the Debutanizer column are subjected to gasification in a gasification reactor. The products of the gasification comprise hydrogen and CO.sub.2. The hydrogen is directed into the hydrogen feed chamber and the CO.sub.2 is directed into the CO.sub.2 feed chamber. The products of the gasification comprising hydrogen and CO.sub.2 are used as additional feed for producing the methanol in the methanol reactor. At a step 1026, the Deethanizer bottom fraction that is rich in C.sub.3+ hydrocarbons and a Debutanizer overhead vapor fraction rich in butane and butylene are treated in a Depropanizer column to produce a Depropanizer overhead vapor fraction that is rich in propane and propylene and a Depropanizer bottom fraction that is rich in C.sub.4+ hydrocarbons. The Depropanizer bottom fraction may also have a considerable amount of C.sub.5 to C.sub.9 hydrocarbons (olefins+paraffins) and aromatic hydrocarbons. A portion of the Depropanizer bottom fraction is directed into the isothermal Methanol-to-Olefin (MTO) reactor for MTO reaction. Remaining portion of the Depropanizer bottom fraction is directed to the gasification reactor for gasification. At a step 1028, the propylene is separated from propane in the Depropanizer overhead vapor fraction in a C.sub.3 splitter column. The propane from the C.sub.3 splitter column is directed along with the fraction of separated hydrocarbons from the Debutanizer column in the gasification reactor for gasification.
[0115] Modifications to embodiments of the present disclosure described in the foregoing are possible without departing from the scope of the present disclosure as defined by the accompanying claims. Expressions such as “including”, “comprising”, “incorporating”, “have”, “is” used to describe, and claim the present disclosure are intended to be construed in a non-exclusive manner, namely allowing for items, components or elements not explicitly described also to be present. Reference to the singular is also to be construed to relate to the plural.
[0116] It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above.
