IT202100012551A1 - CO2 CONVERSION PROCESS - Google Patents

Description

Text attached to the patent application for an industrial invention entitled:

?CO2 CONVERSION PROCESS?

The present invention ? relating to a conversion process of CO2, pure or contained in gaseous streams of various kinds through the use of an E-RWGS (electrified Reverse Water Gas Shift) reactor. Pi? specifically, the innovative process object of the present invention refers to a solution for the transformation of gases containing CO2 into gases containing carbon monoxide (CO) and Hydrogen (H2), molecules which constitute the building blocks of important activities? for the production of chemicals, fertilizers and fuels. This solution therefore aims to contribute to the reduction of the concentration of GHG (Green House Gas) through the removal and transformation of their main component, CO2, and its reintegration into production cycles.

DESCRIPTION OF THE STATE OF THE ART

The reduction of the concentration in the atmosphere of GHGs whose main components are carbon dioxide (CO2) and methane (CH4), requires more use? efficiency of primary energy sources, an increase in the share of use of renewable energies and a decrease in the use of hydrocarbon sources. With the increase in the production of electricity obtained from renewable sources will it promote? the diffusion of the processes of electrolysis of the water that will make available relevant quantities of H2 that will come? used in a supply chain in which it will participate? both with the function of energy carrier and with that of chemical reagent.

In parallel, the conditions for the industrial use of electrified reactor solutions will be developed to replace those of thermal reactors.

CO2, what? primarily generated by the combustion of hydrocarbons, it has reached a concentration of 415 ppm in the atmosphere and is the component pi? abundant among GHGs. Its use as a source of carbon and oxygen? then one of the topics pi? relevant to address to improve sustainability? of the activities? anthropic and avoid the increase of the temperature of the anthroposphere.

Was the problem already? clearly evident in the 80s and 90s as. Can you? cite for example the work described in Energy & Fuels (1996, 10, 305-325) which includes an extensive analysis of the paths of use of CO2 considering both:

i) its properties? physical (eg for supercritical extraction, Enhanced Oil Recovery, use as an inert gas in fire management and other safety related applications);

ii) its chemical transformations (for example in the production of acids, alcohols and derivatives, urea and derivatives, polycarbonates).

And yet, still, today much less than 1% of the world's CO2 production is reused.

Also one of the most interesting, huh? that of its integration in the production of Methanol (MeOH), which pu? be used both in the industrial chemical and in the energy supply chains (see for example WO 2020/058859 A1) in internal combustion engines, it is not yet? been developed.

Clearly the difficulty? more relevant has thermodynamic reasons, as the CO2 ? the final product of most of the activities? anthropic: i) those necessary for life (one kilo of CO2 is emitted every day with breathing, which is equivalent to 2.5 billion tons emitted by the entire human race every year), ii) those dedicated to industrial processes of production and use of energy, iii) those of the production of the chemical industry. Overall, these last two types of activity? produce approx. 40.5 billion tons of CO2 per year (see for example https://www.ispionline.it/it/pubblicazione/co2-daproblema-risorsa-29429). However this situation can be modified by defining specific solutions for the use of CO2 emissions.

In particular yes? intensive development of solutions has been launched which will make available large quantities of electricity produced from renewable sources (sun, wind and hydroelectric energy). It is also mentioned that the European Union (EU Green Deal https://ec.europa.eu/commission/presscorner/detail/it/IP_ 19_6691) targets the use of electricity produced from renewable sources through the electrolysis of ?water and therefore for the production and use of H2. AND? however it is also true that, in parallel, the reduction of GHGs will have to consider both the reduction of CO2 emissions and its separation and reuse.

These solutions can follow both the Carbon Capture and Sequestration (or Storage, CCS) and Carbon Capture and Utilization (CCU) approaches.

If the CCS pu? become economically attractive when the ?carbon tax? exceeds threshold values, the solution of storing this molecule in exhausted or nearly depleted reservoirs does not guarantee, however, in most contexts, permanent removal of the molecule and a significant reduction in emissions. The CCS is therefore proposed as a transitory solution and suitable for specific contexts in which both storage solutions and the possibility are available. to recover CO2 from the emissions of the activities? industries, which is not always feasible.

SUMMARY OF THE PRESENT INVENTION

The Applicant believes that the CCU solutions in which the CO2 ? reused in the production cycle, are much more? effective and applicable in an extensive way and are, among other things, integrable in a more? effective with activities of production and use of H2, in particular those that produce it through water electrolysis processes.

In this regard, it should be remembered that the production of hydrogen and its use in reactions with CO2 can be directed to produce:

i) Synthetic Natural Gas (SNG);

ii) Methanol (MeOH) and its derivatives;

iii) Ammonia/Urea;

iv) Liquid hydrocarbons.

However it must be highlighted that the direct hydrogenation of CO2 in SNG, MeOH and liquid hydrocarbons ? energetically not very effective and not very selective (e.g. approx. 30-40% v/v of the hydrogen used in the synthesis of MeOH from CO2 is transformed into H2O and to a lesser extent into CH4) and as regards the production of MeOH, of liquid hydrocarbons solutions are used in a still prototype phase. On the other hand, a rapid development of solutions using electrolytic hydrogen in the synthesis of ammonia/urea is expected.

Pi? in detail, in the case in which MeOH, hydrocarbon compounds are to be produced, the Applicant has found and ? The object of the present invention is that it is preferable to introduce a step of E-RWGS (Electrified Reverse Water Gas Shift) into the production chain and produce synthesis gas (a mixture which mainly contains H2 and CO) in a much more efficient way. effective through reactions [1] and [2] instead of reaction [3] alone.

The combined process of reactions [1] and [2] pu? also use widely used industrial solutions of which ? well known the feasibility? technical and economic.

CO2 H2 ? CO H2O (?H = 42 kJ/mol) [1] CO 2 H2 ? CH3OH (?H = - 89 kJ/mol) [2] CO2 3 H2 ? CH3OH H2O (?H = -48 kJ/mol) [3] CO2 4 H2 ? CH4 2H2O (?H = - 164 kJ/mol) [4] CO 3 H2 ? CH4 H2O (?H = - 206 kJ/mol) [5] The present invention ? therefore relating to a conversion process of CO2, pure or contained in gaseous streams of various kinds through chemical processes which include the use of an electrified E-RWGS (Reverse Water Gas Shift) reactor.

Pi? specifically, the innovative process object of the present invention refers to a solution for the transformation of gases containing CO2 into gases containing carbon monoxide (CO) and H2, molecules which constitute the bricks of important activities? production of chemicals, fertilizers and fuels.

In one aspect, the present invention provides a process, as defined above, in which the transformation of CO2 which takes place in the electrified E-RWGS reactor uses as a reactant H2 produced by electrolysis processes or made available as a by-product by various industrial processes.

In a further aspect, the present invention provides a process, as defined above, in which electricity necessary for E-RWGS and/or electrolysis processes? produced from renewable sources.

In another aspect, the present invention provides a process, as defined above, in which the electrified E-RWGS reactor integrates into process schemes:

- for the production of MeOH and its derivatives which can be used in the chemical and energy sectors;

- in process schemes where ? including a Fischer-Tropsch stage for the production of liquid hydrocarbons that can be used in the chemical and energy sectors;

- in process schemes using Bio-Gas for the production of MeOH from CO2 and Bio-CH4;

- in process schemes for the production of Methanol, its derivatives and/or liquid hydrocarbon compounds, using Acid Natural Gas (rich in CO2) and/or other off-gases of industrial processes with a high CO2 content;

- in process schemes for the production of blue-H2 through the production of synthesis gas with the technologies of Steam Reforming (SR), Autothermal Reforming (ATR), Combined Reforming (CR) and in particular of Catalytic Partial Oxidation (CPO) ; followed by a stage of Water Gas Shift (WGS) and separation of the H2 from the current containing the CO2 that pu? be used to power an E-RWGS stage and reintegrated into a production cycle of chemical or energy products;

- in process schemes for the production of MeOH or liquid hydrocarbons, using the Fischer-Tropsch process, in which synthesis gas production processes are used such as Steam Reforming (SR), AutoThermal Reforming (ATR), Combined Reforming (CR) and in particular Catalytic Partial Oxidation (CPO) which make concentrated CO2 currents available as a by-product.

In the process of the present invention the E-RWGS reactor is operated at pressures between 10 and 100 atm (1.10 MPa and 10.13 MPa) and preferably at pressures between 30 and 80 atm (3.04 MPa and 8.11 MPa ) and temperatures ranging from 500 to 1000°C and preferably at temperatures ranging from 650 to 950°C.

BRIEF DESCRIPTION OF THE FIGURES

Further characteristics and advantages of the process of the present invention will appear later on. clear from the following description, set out with reference to the attached figures which illustrate at least one non-limiting embodiment thereof.

In particular:

- figure 1 illustrates the simplified block diagram that integrates the unitary operations of electrified E-RWGS, H2 production through water electrolysis processes (Solid Oxide Electrolysis Cell ? SOEC, Alkaline Electrolyzer ? AE, Polymer Electrolyte Membrane Electrolyzer ? PEME) and MeOH synthesis according to the present invention;

- figure 2 illustrates the simplified block diagram integrating the unitary operations of electrified E-RWGS, H2 production through water electrolysis processes (Solid Oxide Electrolysis Cell ? SOEC, Alkaline Electrolyzer ? AE, Polymer Electrolyte Membrane Electrolyzer ? PEME) and synthesis of liquid hydrocarbons by the Fischer-Tropsch process;

- figure 3 illustrates a simplified block diagram of the CAMERE process described in Ind. Eng. Chem. Res. 1999, 38, 1808-1812;

- figure 4 illustrates the simplified block diagram of a process which allows to obtain Bio-CH4 and MeOH obtained from renewable sources from bio-gas and which, with the exception of the CO2 produced to obtain electricity, is configured as a negative emissions of CO2; - figure 5 illustrates the simplified block diagram of a process which allows to obtain Hydrogen through the CPO process (Catalytic Partial Oxidation) and a stream of CO2 which through the unit? of E-RWGS is transformed into synthesis gas which is used in the production of MeOH which, apart from the CO2 produced to obtain electricity, is configured as a process with negative CO2 emissions;

- figure 6 illustrates the simplified block diagram of a process which allows to obtain Hydrogen through the CPO process and a stream of CO2 which through the unit? of E-RWGS is transformed into a synthesis gas with the appropriate composition to obtain the production of Liquid Hydrocarbons through the Fischer-Tropsch synthesis and which, apart from the CO2 produced to obtain electricity, is configured as a process with negative emissions of CO2;

- figure 7 represents the process flow diagram of the production process of Example 1, sheet 1, in which:

? C-01: ? the H2 supply compressor;

? R-01: ? the electrified reactor of RWGS;

? HX-03: ? the low temperature heat recovery exchanger;

? HX-04 ? the final syngas cooler;

? C-02 ? the CO2 supply compressor; ? HX-01 ? the RWGS reactor feed/product recovery unit;

? V-01 ? the first H2O separator;

? V-02 ? the second H2O separator;

? HX-02 ? the high pressure steam generator; ? HS ? High Pressure Steam;

? LS ? Low Pressure Steam;

? HW ? High Pressure Boiler Feed Water;

? LW ? Low Pressure Boiler Feed Water;

? CWS ? Cooling Water supplies;

? CWR ? cooling water return;

? P.W.? Produced Water;

- figure 8 represents the process flow diagram of the production process of Example 1, sheet 2, in which:

? HX-05 ? the recovery unit charges MeOH product; ? R-02 ? the MeOH synthesis reactor;

? C-03 ? the recirculation compressor;

? HX-06 ? the MeOH capacitor;

? V-03 ? the MeOH high pressure separator;

? V-04 ? the MeOH low pressure separator; ? HG ? High Pressure Steam;

? HW ? High Pressure Boiler Feed Water;

? CWS ? Cooling Water Supply;

? CWR ? Cooling Water Return.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

Before describing in detail the preferred embodiments of the present invention or details of the same, it is considered useful to specify that the related scope of protection does not limited to the particular embodiments described below. The disclosure and description herein are illustrative and explanatory of one or more currently preferred embodiments and variants, and will result? clear to those skilled in the art that various changes in design, organization, order of operation, means of operation, equipment structures and location, methodology and use of mechanical equivalents may be made without thereby being alien to the spirit of the invention. because many different and distinct embodiments can be made within the concepts taught here, and since? there are many modifications that can be made to the embodiments described herein, it must be understood that the details provided below must be interpreted as illustrative and not limiting of the spirit of the invention.

Again with reference to Figure 1, the block diagram describes for example one of the innovative conceptual solutions object of the present invention. In this case a gaseous stream containing CO2 is mixed with hydrogen produced by an electrolyser and is sent to an electrified reactor where the E-RWGS reaction takes place so as to produce a mixture of syngas suitable for the synthesis of methanol.

Similarly, Figure 2 describes a process solution in which the E-RWGS reactor is integrated into a scheme in which liquid hydrocarbons are produced by means of the Fischer-Tropsch (FT) synthesis. Also in this case a gaseous stream containing CO2 is mixed with hydrogen produced by electrolysis and sent to the electrified reactor of E-RWGS in order to obtain a syngas with a composition suitable for the Fisher-Tropsch synthesis and therefore for the production of ?liquid hydrocarbons

In one aspect of the present invention, among the electrified reactors which can be conveniently used in the process, the ?resistance-heated reactors? in which the catalyst ? heated by the Joule effect as for example described in the article published in Science 364, (2019), 756?759. This solution makes it possible to significantly reduce the radial temperature gradients through the catalyst layer and to transfer the heat much more quickly. effective than what happens in thermal SR reactors that use furnaces that are strong emitters of CO2, the heat to the zone in which strongly endothermic reactions take place, such as the following [6].

CH4 H2O ? CO 3H2 (?H = 206 kJ/mol) [6]

Pi? in detail it is reported that the effectiveness of heat transfer in electrified reactors goes from approx. 50% (typical value of thermal reactors) to pi? by 90% depending on the solutions that are adopted. At the same time, the possibility of avoiding heating furnaces, allows to drastically reduce the dimensions of the reactors and the emissions of CO2 into the atmosphere.

Among the electrified reactors which can be conveniently used in the process of the present invention, are also included the ?induction-heated reactors? which exploit the electromagnetic induction heating of an electrically conductive object through the heat generated inside the object itself by eddy currents (edge current). This type of reactor is described e.g. the publication, Ind. Eng. Chem. Res., 56 (2017) 14006?14013, which experimentally demonstrates the possibility to carry out the SR reactions in a reactor containing catalysts based on Nickel?Cobalt nanoparticles. The co-component of the catalyst with a high Curie temperature, ? in this case capable of transferring the necessary heat to the reaction environment.

These solutions adopted eg. for the SR reaction, which requires high temperatures and pressures, can be extended and developed even more? advantageous for electrified E-RWGS processes where chemical reactions require about 1/5 of the heat required for SR processes.

Table 1 summarizes the comparison values between consumption and emissions per ton of methanol produced with:

i) the best conventional processes (Best Available Technologies ? BAT) using natural gas, ii) direct hydrogenation processes of CO2 using H2 produced by the electrolysis of H2O iii) methanol production processes with the present process invention in which an intermediate stage of E-RWGS is included (see Example 1) and H2 produced by the electrolysis of H2O is used.

TABLE 1

(A) BAT ? Best Available Technologies (i) CHEMSYSTEMSPERP PROGRAM Methanol 07/08-2 November 2008 revised and updated and (ii) Methanol: The Basic Chemical and Energy Feedstock of the Future, Asinger's Vision Today, Editors:

(B) E-MeOH via direct hydrogenation of CO2 (Appl. Energy 233-234 (2018) 1078-1093)

(C) MeOH via E-RWGS (see Example 1)

From the table it can be seen that the process of the present invention allows a considerable advantage in the Carbon Efficiency values (moles of carbon introduced into the process/moles of carbon converted into MeOH) both compared to the production of MeOH obtained by direct hydrogenation of CO2 using hydrogen produced by electrolytic means (processes also called E-MeOH) but also with respect to the production processes of MeOH from Natural Gas. The process of the present invention also allows to reduce CO2 emissions more? of an order of magnitude compared to those of the other reference technological solutions.

The Energy Efficiency and Carbon Efficiency values are mainly influenced by the quantity? and from the quality? of electricity consumed in the electrolysis processes (see Example 1) and obviously make the technological solution more? advantageous in contexts in which a surplus of electricity is used which would otherwise be difficult to use and/or in contexts in which renewable electricity is available.

The process of the present invention is compared with a known solution, studied since the end of the 90s of the last century and called CAMERE (CO2 Hydrogenation to form Methanol via a Reverse-Water-Gas-Shift Reaction; published in Ind. Eng. Chem. Res. 38 (1999) 1808-1812). The process, illustrated in Figure 3, consists of two sections; in the first, a mixture containing CO2 and H2 enters a thermal reactor of RWGS at ca. 500°C and 10 atm (1.01 MPa) producing CO and H2O according to the previously described equation [1]. Subsequently the water is separated and the gaseous mixture for 40% is recycled, while the remaining 60% v/v, which must have a composition in which the ratio (H2-CO2)/(CO+CO2) ? approximately equal to 2 v/v, it is sent to the subsequent compression and then synthesis section of the MeOH which in the CAMERE process is carried out at a temperature of 250°C and at a pressure of 30 atm (3.04 MPa).

However, the ROOMS process, which has reached the pilot plant stage, is not never been developed on an industrial scale. Industrially, the RWGS thermal reactor should in fact preferably operate at high temperature (greater than 700°C) and low pressure (less than 15 atm) to disfavor the parasitic methanation reactions previously described in equations [4-5].

The industrial thermal reactor would therefore require the use of an oven which would use the combustion of hydrocarbons and which would therefore be an emitter of the same CO2 which it then intends to convert. On the contrary, the synthesis of MeOH ? favored by high pressures (P > 50 atm) and relatively low reaction temperatures (about 250?C). The syngas produced at low pressure in the RWGS would then have to be cooled and compressed with a high expenditure of energy.

For these reasons, as already? mentioned, the process ROOMS ? been tested by operating the thermal reactor of RWGS at ca. 500°C and 10 atm and subsequently compressing the synthesis gas obtained at 30 atm and carrying out the synthesis of MeOH at 250°C. Furthermore, hydrogen? produced from non-renewable sources.

Overall, the ROOMS process does not lead to improvements, either for what? that concerns CO2 emissions, both for ci? that concerns the Carbon Efficiency, both for ci? which concerns energy efficiency, compared to ?conventional? processes? of MeOH production which use Natural Gas (NG) and involve the production of synthesis gas with the Steam Reforming (SR), AutoThermal Reforming (ATR) and Combined Reforming (CR), non-Catalytic Partial Oxidation (POx) technologies described in example in:

- ?Technologies for large-scale gas conversion?,

Applied Catalysis A: General, 221 (1-2), p.379, Nov 2001;

- ?Synthesis Gas production by Steam Reforming?,

EP1097105A1;

-Adv. Catal. 47 (2002), p. 65?139;

- ?Catalytic Steam Reforming?; Rostrup-Nielsen J.R.; pg 1-117, Catalysis Vol. 5, Edited by

The process, object of the present invention, clearly overcomes the limits of the known CAMERE process, using an electrified E-RWGS reactor which can operate at high temperature, between 650°C and 1000°C (under conditions in which the methanation reaction [4-5] is inhibited) and preferably between 700°C and 950°C and at high pressure between 25 and 100 atm (2.53 MPa and 10.13 MPa) and preferably between 30 and 80 atm (3.04 MPa and 8.11 MPa).

Furthermore, the process object of the present invention provides for the use of hydrogen sources (AE, SOEC, PEME) produced through hydrolysis processes which preferably use renewable energy or electrical energy surplus or coming from other industrial processes which do not use it directly.

The process of the present invention also provides for the possibility to use the CO2 separated from various hydrocarbon sources (for example biogas and acid gases) or obtained as a by-product of various industrial processes (for example those from which bluehydrogen can be obtained).

For example, Figure 4 shows a diagram in which the treated CO2 stream comes from bio-gas which in this way allows to obtain a stream of Bio-Methane (Bio-CH4) and Bio-MeOH from renewable sources.

Pi? in particular, the scheme in Figure 4 allows for the production of Bio-CH4 and Bio-MeOH with negative emissions of CO2 less than that emitted in the production of electricity. If the latter is obtained completely or at least in part from renewable sources or if it is taken from a context that produces it in excess, the scheme configures a process with negative CO2 emissions.

Figure 5 instead shows a simplified block diagram in which a Blue-Hydrogen production process (such as the one described in US2012/031391 A1 in which a stream of hydrogen and a stream with a high concentration of CO2 are obtained) is integrated with one step of E-RWGS and MeOH synthesis.

Figure 6, on the other hand, shows a simplified block diagram in which a Blue-Hydrogen production process (such as the one described in US2012/031391 A1) in which a stream of hydrogen and a stream with a high concentration of CO2 are obtained, it is integrated with a stage of E-RWGS and Fischer Tropsch (F-T) synthesis of liquid hydrocarbons.

The schemes of Figures 5 and 6 include, in particular, a Catalytic Partial Oxidation (CPO) technology (in the following pages are included the references of 16 patents and 5 publications describing the technology) with low contact time which allows to produce syngas without using pre-heating ovens and therefore particularly suitable for confining all CO2 emissions in the process gas from which it can? be fully recovered.

The use of this CO2 according to the process of the present invention, in particular in the diagrams shown in figures 5 and 6, which include an E-RWGS reactor, allows to transform all or part of the CO2 emissions into a chemical product or a fuel of renewable origin and therefore also to shift the corresponding share of H2 from blue to green.

The diagrams shown in figures 5 and 6 also envisage using the production of O2 associated with that of H2 in the electrolysis of water, to feed the CPO process with a further improvement in the overall efficiency of the process.

The diagrams of Figures 5 and 6 can be developed by obtaining the production of H2 also through the processes of Steam Reforming (SR), AutoThermal Reforming (ATR) and Combined Reforming (CR) but the use of CPO technology makes them much more ? efficient and drastically reduces CO2 emissions as it eliminates all process ovens.

Which CPO technology are you referring to? described numerous literature documents among which are mentioned:

- WO2020058859 (A1), WO2016016257 (A1), WO2016016256 (A1), WO2016016253 (A1), WO2016016251 (A1), WO 2011151082, WO 2009065559, WO 2011072877 , US 2009127512 , WO 2007045457 , WO 2006034868 , US 2005211604 , WO 2005023710 , WO 9737929, EP 0725038, EP 0640559,

- ?Issues in H2 and synthesis gas technologies for refinery, GTL and small and distributed industrial needs?;

Catalysis Today, 106 (1-4), p.34, Oct 2005, - ?Fuel rich catalytic combustion: Principles and technological developments in short contact time (SCT) catalytic processes?; ; Catalysis Today, 117(4), 384-393; DOI: 10.1016/j.cattod.2006.06.043 Published: OCT 15 2006

- ?Natural Gas Catalytic Partial Oxidation: A Way to Syngas and Bulk Chemicals Production | TechOpen?;

http://dx.doi.org/10.5772/48708

- ?Short Contact Time Catalytic Partial Oxidation (SCT-CPO) for Synthesis Gas Processes and Olefins Production?;

Ind. Eng. Chem. Res. 2013, 52, 17023?17037; https://doi.org/10.1021/ie402463m.

Example 1

Process of converting CO2 to MeOH

There are 15,000 European plants that produce biogas, a mixture that contains about 50% CH4 and 50% CO2 through the anaerobic digestion process. The biomethane obtained after the removal of CO2 is injected into the natural gas network and used, for example, for automotive or electricity generation. This solution ? widely applied throughout Europe and enjoys state subsidies. However, the decline in production costs of renewable energy will allow? to develop new solutions. In particular, solutions that include units? processes dedicated to the reuse of CO2. The small dimensions of the European plants make s? that the available flow rates of CO2 are between 100 and 500 Nm<3>/hour and you can? consider an average value of 300 Nm<3>/hour associated with a biogas plant that produces 1.2 MW of electricity.

The exemplified process combines streams of CO2 from biogas and green H2 from electrolysis to produce MeOH.

In particular yes? developed an economic technical study in which approx. 300 Nm<3>/hour of CO2 and 938 Nm<3>/hour of H2 produced by Polymer Electrolyte Membrane Electrolyzer (PEME). I study ? It was developed using the Aspen Plus V10 software by simulating the literature performances of the RWGS and MeOH synthesis unit operations.

Process diagram

The flowsheet used? represented in Figures 7 and 8. In the scheme adopted both CO2 and H2 are compressed to approx. 50 bar and subsequently the hydrogen is divided into two flows. First mixed with CO2, the mixture is heated to 650?C before entering the E-RWGS reactor which is assumed to operate at 950?C. The reactor outlet stream containing CO2, H2, CO, H2O and CH4 is cooled to 20°C to remove the water produced by the E-RWGS reaction. What is the gaseous stream? obtained ? mixed with Hydrogen to adjust the Methanol (SN) modulus of the syngas

SN = (H2-CO2)/(CO+CO2)

The syngas what? obtained ? mixed with the recycle stream of the MeOH synthesis section and heated to 250°C before entering the MeOH synthesis reactor which operates at approx. 50 bars. The reaction product is cooled to 25°C to separate the mixture of Water and MeOH from the species which remain gaseous. 10% v/v of the gaseous stream is purged to avoid the accumulation of by-products (e.g. CH4) while the rest ? recycled to the MeOH synthesis reactor.

unit? by E-RWGS

The reactor operates at equilibrium at 950°C and 50 atm using a Ni/Al2O3 catalyst and a gas hour space velocity (GHSV) equal to 5000 NL/(kg x hour). The power supply uses a ratio of H2/CO2 = 2v/v.

The design of the reactor considers its electrification with a heat transfer efficiency generated by the Joule effect of 90%. In situ heat generation in the reaction environment minimizes heat transfer limitations. This situation is obtained by using, for example, a monolith of FeCrAl in the shape of a high resistivity knitted gauze as a support in the catalytic bed. on whose surface? active phase deposited.

The resistivity inside the catalytic bed is maximized by dispersing the networks between ceramic materials which avoid electrical short circuit and at the same time allow the reaction mixture to pass through the catalytic bed. Power loading is achieved by minimizing current flow using low voltage and high amperage.

MeOH synthesis reactor

The reactor operates at 50 bar and at an isothermal temperature of 250?C and ? been simulated as an equilibrium reactor with approach temperatures of 10?C. The simulation results were compared with those of an industrial reactor using a commercial Cu/ZnO/Al2O3 based catalyst and operating with a GHSV of 8,000 NL/(kg x hour). The purge on the recycle gas ? been obtained by inserting a? unit? of Pressure Swing Adsorption (PSA) which allows 90% of the hydrogen to be recovered and reinserted into the synthesis loop.

Results

Tables 2-9 include information on material and energy balances and on the main process conditions.

Table 10 includes the total consumption of materials and energy for two cases in which;

Case A: no purge is used in the Methanol synthesis loop, 7.5% v/v Methane input and 9.5% v/v Methane output (preferred situation)

Case B: 10% v/v Methanol synthesis loop recycle gas ? purged, 5.6% v/v Methane in, 7.1% v/v Methane out. I purge it? burned to produce thermal energy which is used by an Organic Renking Cycle.

(1) referred to pure Methanol

(2) emissions into the atmosphere without energy recovery

(3) without heat recovery

(4) 4.6 kWh/Nm3(H2) consumption

Claims (11)

1. Process for the conversion of pure CO2 or CO2 contained in gaseous streams of various kinds through the use of an electrified Reverse Water Gas Shift reactor (E-RWGS) in which a gaseous stream containing H2 is co-feeded and which is integrated in process schemes leading to the production of fuels and chemicals. 2. Process according to claim 1, wherein the transformation of the CO2, which takes place in the electrified E-RWGS reactor, uses Hydrogen produced by electrolysis processes as the reactant. The process according to claim 1, wherein the transformation of the CO2 takes place in an electrified E-RWGS reactor which uses as a reactant a stream containing Hydrogen which is made available as a by-product by various industrial processes 4. Process according to claims 1?3, in which the electricity? necessary for the RWGS and/or electrolysis processes? produced from renewable sources. 5. Process according to claims 1?4, wherein the electrified E-RWGS reactor is integrated in process schemes for the production of MeOH. 6. Process according to claims 1?4, wherein the electrified E-RWGS reactor integrates into process schemes wherein? including a Fischer-Tropsch stage for the production of liquid hydrocarbons that can be used in the chemical and energy sectors 7. Process according to claims 1-6, wherein the E-RWGS reactor is operated at pressures ranging from 10 to 100 atm and preferably at pressures ranging from 30 to 80 atm and temperatures ranging from 500 to 1000°C and preferably at between 650 and 950?C. 8. Process according to claims 1-7, wherein the reactor of electrified E-RWGS is integrated into process schemes using Bio-Gas for the production of MeOH from CO2 and Bio-CH4. 9. Process according to claims 127, wherein the electrified reactor of E-RWGS ? integrated in production processes of Methanol or liquid hydrocarbon compounds, using Acid Natural Gas, rich in CO2 and/or other off-gases of industrial processes with a high CO2 content. 10. Process according to claims 127, wherein the reactor of electrified E-RWGS is integrated in process schemes for the co-production of H2 and MeOH in which synthesis gas production processes are used such as Steam Reforming, Autothermal Reforming, Combined Reforming and in particular Catalytic Partial Oxidation. 11. Process according to claim 10, wherein the RWGS reactor is electrified integrated in process schemes for the co-production of H2 and liquid hydrocarbons, in which synthesis gas production processes are used such as Steam Reforming, AutoThermal Reforming, Combined Reforming and in particular Catalytic Partial Oxidation and liquid hydrocarbons are obtained through the Fischer-Tropsch process.