Manufacturing chemical products from carbon dioxide with a reduced or negative carbon footprint.

Abstract

The present invention is a carbon dioxide-negative method for producing a polymer product, comprising the following steps: (a) Recovering carbon dioxide from gases containing carbon dioxide, especially from air or exhaust gases (1, 11.1, 11.2); (b) Converting at least a portion of the recovered carbon dioxide into intermediate products containing olefins (2, 12.1); (c) Optionally, the intermediate olefin product is subjected to a derivatization reaction (3, 13.1, 13.2) to obtain an olefin derivative; (d) Further polymerization of olefins and / or olefin derivatives, particularly with at least one additional monomer (4, 14.1, 14.2) to obtain polymer products; Here, in at least step (a), particularly in at least steps (a) and (b), and particularly in all steps (a) to (d), the energy required to carry out the steps of this method is supplied in the form of renewable energy. This concerns carbon dioxide-negative methods for manufacturing polymer products.

Description

[Technical Field]

[0001] The present invention relates to a method for producing polymer products, particularly a method for producing carbon dioxide-negative polymer products. Furthermore, the present invention relates to an apparatus for carrying out the corresponding method, particularly a chemical plant. [Background technology]

[0002] As the world continues to face the challenge of climate change, there is a growing recognition of the importance of reducing carbon emissions across all sectors of the economy. In response to this challenge, many companies are developing CO2-neutral chemical products that produce no net carbon dioxide emissions into the atmosphere during their manufacture, use, and disposal.

[0003] CO2-neutral chemicals are chemical substances that are manufactured using low-carbon or renewable energy sources and have no net carbon dioxide emissions throughout their lifecycle. This means that the carbon emissions associated with their manufacture and use are offset by removing an equal amount of carbon dioxide from the atmosphere through activities such as carbon capture and storage or the use of renewable energy sources.

[0004] Examples of CO2-neutral chemical products include bioplastics made from renewable sources such as corn starch or sugarcane, which can serve as substitutes for conventional petroleum-based plastics. Other examples include biofuels made from renewable resources such as algae or waste vegetable oil, which can be used as substitutes for fossil fuels in transportation and other applications.

[0005] For example, polyethylene terephthalate (PET) is currently mainly produced from terephthalic acid and ethylene glycol, both petroleum-derived components. Replacing terephthalic acid with frangic acid is known to be advantageous because it allows one component to be produced from renewable raw materials. The second component, monoethylene glycol (MEG), can be produced from bioethanol. However, even using 100% renewable raw materials and renewable energy would only achieve climate neutrality to a certain extent.

[0006] Therefore, attempts have already been made to manufacture so-called CO2-negative products. CO2-negative products are defined as products or technologies that actively remove more carbon dioxide from the atmosphere than they emit during their manufacture, use, and disposal. This means they have a net negative carbon footprint and can help mitigate the effects of climate change.

[0007] In this regard, for example, an initiative toward the production of carbon-negative fuels is described in U.S. Patent Application Publication 2010 / 0311157 A1, which teaches the production of biofuels using algae as a raw material. This process is claimed to be carbon-negative because algae have a high CO2 absorption rate.

[0008] The development of CO2-negative products is an important step toward reducing carbon emissions and mitigating the effects of climate change, but their manufacture presents several challenges. One of the main challenges is the cost of implementing these technologies, which can be extremely high and may require significant investment in research and development.

[0009] Another challenge is scaling up these technologies, because many of the CO2-negative products currently known are still in the early stages of development and may not be able to be manufactured on a large scale. In addition, the energy and resources required to manufacture CO2-negative products may offset their carbon-negative benefits, especially if renewable energy sources are not used.

[0010] Therefore, an improved solution that at least partially overcomes the aforementioned shortcomings is still needed. [Overview of the Initiative] [Problems that the invention aims to solve]

[0011] Therefore, an object of the present invention is to create an improved method for producing chemical products, particularly polymer products, with the lowest possible carbon footprint. In particular, this method should enable the production of CO2-negative chemical products in a cost-effective, scalable, and / or efficient manner. [Means for solving the problem]

[0012] Specifically, the core of the present invention relates to a method for producing polymer products, in particular a carbon dioxide-negative method, the method comprising the following steps: (a) Recovering carbon dioxide from gases containing carbon dioxide, especially from air or exhaust gases, especially by direct air recovery; (b) Converting at least a portion of the recovered carbon dioxide into intermediate products containing or derived from olefins, particularly ethylene and / or propylene, preferably by: (i) electrochemical reduction of carbon dioxide in the presence of water; and / or (ii) Hydrogenating carbon dioxide with hydrogen to form methanol, and then, preferably, converting the methanol to an olefin as follows: - Methanol-olefin reaction (MTO); and / or - Methanol-gasoline reaction (MTG); (c) Optionally, the intermediate olefin is derivatized to obtain an olefin derivative, such as glycol and / or acrylonitrile; (d) Further polymerization of olefins and / or olefin derivatives, particularly with at least one additional monomer, to obtain a polymer product; Here, preferably, in at least step (a), particularly in at least steps (a) and (b), and particularly in all steps (a) to (d), the energy required to carry out the above steps of this method is supplied in the form of renewable energy.

[0013] Most preferably, the method of the present invention is a carbon dioxide-negative method. This means that, in particular, when this method is implemented, it removes more carbon dioxide from the environment, for example from the atmosphere, than is emitted during the manufacturing process of the polymer product.

[0014] However, in principle, this method can also be implemented in a carbon dioxide-neutral manner, for example, in a carbon dioxide-neutral manner, or in a manner in which more carbon dioxide is emitted during the manufacturing process of the polymer product than is removed from the environment, particularly from the atmosphere, by this method.

[0015] The present invention provides an effective, inexpensive, sustainable, and stable method for producing polymer products with a low or even negative carbon footprint. Through a combination of the process steps of the present invention, the method can be implemented without the use of any fossil raw materials or fossil energy sources.

[0016] The method of the present invention is also highly modular. This means that the individual method steps can be carried out at one and the same location or plant, or the individual method steps can also be carried out at different locations. For example, steps (a) and (b) can be carried out, for example, in regions with a high solar radiation dose. The olefins produced in this way can then be transported to other locations where facilities for carrying out further method steps already exist.

[0017] The method of the present invention can be carried out particularly advantageously in the sunbelt, along the equator, between the northern and southern turn radii, and / or in deserts. In these locations, almost any amount of solar energy, i.e., the solar radiation energy that can be utilized by solar power cells and / or the solar thermal energy that can be made available by solar thermal collectors, is available.

[0018] Particularly preferably, the energy required to carry out the method steps is particularly electricity and / or heat. The energy required in the form of electricity is generated particularly by solar power units and / or wind power units, and / or the energy required in the form of heat is generated particularly by solar thermal collectors. However, other forms of energy can also be used.

[0019] Thus, in a further preferred embodiment, the method of the present invention includes a further method step of generating renewable energy, particularly using solar power units and / or wind power units and / or solar thermal collectors.

[0020] In particular, the required energy is generated at the same location where step (a), particularly steps (a) and (b), or all steps are carried out, particularly in the same plant.

[0021] The carbon dioxide recovered in process (a) is used, at least in part, to produce polymer products and / or further chemical substances. Additionally, a portion of the recovered carbon dioxide can, if desired, be further converted to solid carbon.

[0022] Specifically, in process (a), carbon dioxide is recovered by a process known as "direct air capture" (DAC).

[0023] Direct air capture is a technology that directly removes carbon dioxide from ambient air using dedicated machinery. DAC technology typically involves passing air through a filter and / or solution that selectively captures CO2, after which the CO2 is isolated, stored, and / or utilized in other processes.

[0024] With respect to the present invention, direct air capture has been found to be particularly beneficial because it is cost-effective and can directly recover CO2 from point sources such as power plants or industrial facilities where process (b) or further method steps are performed.

[0025] Particularly preferably, the recovery of carbon dioxide in process (a) is carried out using a chemical absorbent or adsorbent, particularly an alkaline substance, such as an alkali or alkaline earth hydroxide in solid or liquid form.

[0026] Advantageously, in method step (a), in a first stage, a gas containing carbon dioxide is contacted with sodium hydroxide, particularly a sodium hydroxide solution and / or solid sodium hydroxide, to absorb the carbon dioxide and form sodium carbonate.

[0027] Specifically, the capture of carbon dioxide from ambient air and / or an exhaust gas stream with a slightly elevated carbon dioxide concentration can be established by the use of low-cost sodium hydroxide, for example, a concentrated caustic soda aqueous solution that is readily available in the market and / or can be obtained on-site from seawater using the brine and electrolysis processes of a water desalination plant.

[0028] In relation to the present invention, "caustic soda aqueous solution" or "caustic soda" is intended to refer to an aqueous solution of sodium hydroxide. In particular, the caustic soda aqueous solution is a concentrated caustic soda aqueous solution, a saturated caustic soda aqueous solution, or a supersaturated caustic soda aqueous solution.

[0029] A sodium hydroxide aqueous solution with a sodium hydroxide concentration of at least 10 mol / l is also called a concentrated sodium hydroxide aqueous solution. On the other hand, at room temperature, the sodium hydroxide concentration of a saturated sodium hydroxide aqueous solution is approximately 32 mol / l, and sodium hydroxide aqueous solutions with higher concentrations are called supersaturated sodium hydroxide aqueous solutions. The saturation concentration changes with temperature.

[0030] For example, in the first step of process (a), the aqueous solution of caustic soda or the aqueous solution of sodium hydroxide has a sodium hydroxide concentration of 1 to 32 mol / l, particularly 10 to 19 mol / l.

[0031] In the second step of step (a), gaseous carbon dioxide and a solution of sodium hydroxide, particularly sodium hydroxide, can then be formed from the sodium carbonate obtained in the first step and / or from the sodium bicarbonate converted from the sodium carbonate obtained in the first step. Therefore, the second step is carried out at a temperature of less than 350°C, preferably less than 250°C, for example, 50 to 200°C, more preferably 90 to 200°C.

[0032] The method of the present invention may consume a large amount of energy required at low temperature levels in step (a). Heat at levels below 350°C is practically unlimited in quantity from solar thermal energy, is CO2 neutral, and inexpensive. In this particular embodiment described above, the decomposition of sodium carbonate is carried out at low temperatures (below 350°C), preferably using heat from solar thermal energy and / or waste heat. However, it is also possible to use thermal energy generated through other energy sources, such as photovoltaic power, wind power, and / or conversion of other energy sources.

[0033] In particular, the second stage of process (a) is carried out according to one of the following procedures I, II, and / or III: I. The sodium carbonate obtained in the first step is supplied in solid form and is at least partially thermally decomposed, thereby releasing gaseous carbon dioxide, and the sodium hydroxide obtained by the thermal decomposition is preferably extracted with an extractant, particularly in parallel with the thermal decomposition of sodium carbonate; II. The sodium carbonate obtained in the first step is supplied as an aqueous solution, and by heating this aqueous solution, particularly to a temperature below the boiling point of the aqueous solution, the sodium carbonate is at least partially thermally decomposed, thereby releasing gaseous carbon dioxide from the solution; III. The sodium carbonate obtained in the first stage is supplied as an aqueous solution and, by the arrangement of an ion-selective membrane, is separated at least partially into sodium bicarbonate and sodium hydroxide. Then, in the third stage, the obtained sodium bicarbonate is at least partially thermally decomposed into carbon dioxide and sodium carbonate.

[0034] In particular, in the method of the present invention, calcium compounds, especially calcium hydroxide, are not used in step (a).

[0035] In the method of the present invention, more preferably, potassium compounds, particularly potassium hydroxide, are not used in step (a).

[0036] Furthermore, preferably, a microporous hollow fiber membrane is not used in step (a).

[0037] In particular, the sodium carbonate obtained in the first step of step (a) can be temporarily stored for, for example, at least 1 minute, at least 1 hour, at least 1 day, at least 1 week, or at least 1 month before being used in the second step. For this reason, sodium carbonate can be stored, for example, in solid form and / or aqueous solution form.

[0038] In particular, the first stage is carried out in such a way that water loss, especially water loss into the atmosphere, is essentially avoided. This can be achieved in particular by using a sufficiently high amount or proportion of sodium hydroxide.

[0039] In a first preferred embodiment, in the first step, a gas containing carbon dioxide is brought into contact with solid sodium hydroxide particles, particularly powdered sodium hydroxide.

[0040] Therefore, gases containing carbon dioxide and moisture, especially residual moisture, are used. Typically, this applies, for example, when air or exhaust gas is used as the carbon dioxide-containing gas in the first stage. This makes it possible to generate a caustic soda aqueous solution in situ, which can react with carbon dioxide in a highly efficient manner. Furthermore, under these conditions, no additional water is required.

[0041] However, if desired, the carbon dioxide-containing gas may be brought into contact with solid sodium hydroxide particles, particularly powdered sodium hydroxide, in the presence of additional water vapor, especially by humidifying the carbon dioxide-containing gas.

[0042] In particular, solid sodium hydroxide particles are brought into contact with a gas containing moisture, especially residual moisture, and in particular, a caustic soda aqueous solution is brought into contact with it, especially a concentrated caustic soda aqueous solution is formed, and during and / or after the formation of the caustic soda aqueous solution, the resulting caustic soda is brought into contact with a gas containing carbon dioxide to produce sodium carbonate. The gas containing moisture may be, for example, a gas containing carbon dioxide to be brought into contact with sodium hydroxide, and / or another gas containing moisture.

[0043] According to a second highly beneficial embodiment, in the first step, a gas containing carbon dioxide is brought into contact with a sodium hydroxide solution, particularly an aqueous solution of caustic soda, to form sodium carbonate. In particular, the aqueous solution of caustic soda is a concentrated aqueous solution of caustic soda, a saturated aqueous solution of caustic soda, or a supersaturated aqueous solution of caustic soda.

[0044] In particular, aqueous solutions of caustic soda have sodium hydroxide concentrations of 1 to 32 mol / l, especially 10 to 19 mol / l. This is one of the possibilities for obtaining sodium carbonate in a highly efficient manner. This allows for the direct use of aqueous solutions of caustic soda, which are inexpensive and readily available from the market, without further processing.

[0045] In the second step of step (a), gaseous carbon dioxide and a sodium hydroxide solution, particularly an aqueous solution of sodium hydroxide, are formed from the sodium carbonate obtained in the first step and / or from the sodium bicarbonate converted from the sodium carbonate obtained in the first step at a temperature of less than 350°C, preferably less than 250°C, and more preferably 90°C to 200°C.

[0046] Preferably, the sodium hydroxide solution obtained in the second step, in particular, is returned to the first step of step (a) and reused. Preferably, the sodium hydroxide solution is concentrated before being returned. However, the sodium hydroxide may be used for other purposes.

[0047] Ideally, the thermal energy required in the second stage is supplied in the form of heat from solar thermal collectors, solar thermal energy plants, and / or waste heat.

[0048] Accordingly, the method of the present invention further includes obtaining heat from a solar thermal collector, a solar thermal energy plant, and / or waste heat, and supplying that heat in the second step of step (a) to a thermal composition of sodium carbonate and / or sodium bicarbonate converted from sodium carbonate obtained in the first step.

[0049] In the second step, procedure I, sodium carbonate is supplied in a solid state, for example, by precipitation of sodium carbonate from caustic soda in the first step, and is thermally decomposed to release gaseous carbon dioxide. Preferably, the decomposed sodium carbonate exists in the form of particulate matter, such as powder.

[0050] In Procedure I, sodium hydroxide (NaOH), which is produced during the thermal decomposition process of sodium carbonate (Na2CO3), is extracted. This extraction further accelerates the decomposition process, thereby enabling complete decomposition.

[0051] In a preferred embodiment of Procedure I, water is used as the extractant, thereby preferably causing at least partial precipitation of sodium carbonate and leaving sodium hydroxide in the solution. In another preferred embodiment, an aqueous solution of a water-soluble alcohol, preferably a water-soluble primary alcohol, more preferably methanol, ethanol, n-propanol, n-butanol, or a mixture thereof, is used as the extractant, thereby preferably causing at least partial precipitation of sodium carbonate and leaving sodium hydroxide in the solution.

[0052] In particular, during and / or after extraction, the extractant in which sodium hydroxide is dissolved is subjected to a separation process, especially distillation, thereby recovering the sodium hydroxide and the extractant.

[0053] In summary, in the second step I for the production of a sodium hydroxide solution from sodium carbonate and the release of carbon dioxide, the release of carbon dioxide from solid sodium carbonate is preferably carried out by direct thermal decomposition, where the final product, the sodium hydroxide solution, is preferably removed by extraction to allow for further decomposition.

[0054] In step II of the second stage of process (a), the sodium carbonate obtained in the first stage of process (a) is supplied as an aqueous solution, and this aqueous solution is at least partially thermally decomposed by heating it to a temperature below the boiling point of the aqueous solution, thereby releasing gaseous carbon dioxide from the solution, particularly by evaporation.

[0055] In particular, the decomposition of sodium carbonate is preferably carried out by heating or boiling an aqueous solution of sodium carbonate to a temperature near the boiling point of the solution at atmospheric pressure.

[0056] Although not essential, the formation of steam bubbles at the bottom of a bottom-heated reaction vessel can significantly contribute to the removal of carbon dioxide from the solution.

[0057] The large surface area of ​​numerous small bubbles, and the long residence time of these bubbles in the solution, increases the release rate. The water vapor is preferably condensed again at the container head, along with heat recovery, and pure carbon dioxide is released. The pure carbon dioxide (wet) is preferably extracted from the gas phase, then dried and may undergo further processing.

[0058] According to the first preferred option, the solution obtained during thermal decomposition is diluted with water, thereby promoting the decomposition of sodium carbonate. This makes it possible to supply a properly diluted sodium carbonate solution during the heating and / or boiling process. Alternatively, a higher concentration sodium carbonate solution can be used, and the solution can be successively diluted during the heating and / or boiling process. This prevents the cessation of carbon dioxide generation.

[0059] In any of the modified methods, the conversion rate can be controlled by the final dilution. The diluted solution mainly contains residues of caustic soda and sodium carbonate and is suitable for direct reuse in the first step of process (a) after concentration by distillation or reverse osmosis, for example.

[0060] According to a second preferred option, an acidic ion exchange resin, particularly a weakly acidic ion exchange resin, is added to the solution to reduce the sodium ion concentration and thereby promote the decomposition of sodium carbonate. In this regard, a weakly acidic ion exchange resin is preferably used to reduce the sodium ion concentration.

[0061] According to a third preferred option, an amphoteric metal compound, particularly an amphoteric metal oxide and / or amphoteric metal hydroxide, is added to the solution to reduce the sodium ion concentration and thereby promote the decomposition of sodium carbonate.

[0062] Amphoteric metal oxides and amphoteric metal hydroxides are insoluble in water but can dissolve in sodium hydroxide solution. In this state, they combine with dissolved sodium ions, lowering the pH and promoting the formation of sodium carbonate. In contrast to protonic acids, which form sodium salts as reaction products, amphoteric compounds dissolved in sodium hydroxide solution can be precipitated and hydrolyzed in a simple and energy-efficient manner, enabling a cyclical process.

[0063] Numerous amphoteric compounds are known. Particularly preferred are aluminum hydroxide, zinc hydroxide, and / or silicon dioxide. These substances are preferred, in particular, because they are readily available and non-toxic. However, other amphoteric compounds can also be used. However, preferably, the amphoteric metal compounds used are one or more of aluminum hydroxide, zinc hydroxide, and silicon dioxide.

[0064] Preferably, the metal hydroxide is aluminum hydroxide, Al(OH)3, and / or zinc hydroxide, Zn(OH)2. Alternatively, these hydroxides can be used directly in a sodium carbonate solution. The amphoteric metal hydroxide combines with sodium ions from the solution to form sodium hydroxometalates, such as sodium tetrahydroxoaluminate, Na[Al(OH)4], and sodium tetrahydroxozinate, Na2[Zn(OH)4].

[0065] In summary, a process is disclosed for recovering carbon dioxide from gases containing carbon dioxide, particularly air or exhaust gases, by absorption into a sodium hydroxide solution and release of CO2 from the formed sodium carbonate, provided that the second step of process (a) follows procedure II, and is further described below: - In the first step of process (a), a concentrated sodium hydroxide solution is used, thereby causing sodium carbonate to precipitate due to exceeding its solubility in the concentrated sodium hydroxide solution during absorption, or a dilute sodium hydroxide solution is used and the solution is concentrated until sodium carbonate precipitates; - The sodium carbonate obtained in the first step of step (a) is dissolved in water, and the carbon dioxide is at least partially thermally decomposed and released by heating and / or boiling in the second step of step (a); - The remaining solution may be concentrated as desired and returned to the first step of step (a).

[0066] In a further aspect of the present invention, an absorption process is proposed for recovering carbon dioxide from a gas containing carbon dioxide, particularly air or exhaust gas, by means of absorption into a sodium hydroxide solution, followed by electrochemically driven disproportionation and thermal decomposition, as follows, according to the second step III of step (a).

[0067] In particular, when following the second step, procedure III, the sodium carbonate obtained in the first step is converted to sodium bicarbonate and caustic soda by disproportionation in the electrochemical apparatus.

[0068] In particular, the sodium carbonate obtained in the first stage is separated at least partially into sodium bicarbonate and sodium hydroxide by an ion-selective membrane. Then, in the third stage, the obtained sodium bicarbonate is at least partially thermally decomposed to carbon dioxide and sodium carbonate. For this reason, the sodium carbonate used in the second stage is supplied in the form of an aqueous solution.

[0069] The caustic soda or sodium hydroxide obtained in the second stage can be supplied back to the first stage, respectively. Meanwhile, the electrochemically generated sodium bicarbonate can be thermally decomposed at temperatures up to 200°C to produce sodium carbonate, carbon dioxide, and water. The sodium carbonate produced in the third stage can then be subjected to electrochemically driven disproportionation again.

[0070] In particular, in this method, electrochemical treatment is used solely to disproportionate sodium carbonate to sodium bicarbonate and sodium hydroxide. The sodium bicarbonate thus obtained is then heated by known methods at a low temperature, such as 50°C to 200°C, preferably from solar heat or waste heat.

[0071] In particular, the ion-selective membrane configuration is preferably a capacitive membrane configuration in which at least the cathode cell, middle cell, and anode cell are separated from each other by a cation-selective membrane.

[0072] In particular, the membrane capacitive configuration comprises a cathode cell, a middle cell, and an anode cell, each separated from the others by a cation-selective membrane. Here, an aqueous solution of sodium carbonate from the first stage is introduced into the middle cell, and a slurry of water and conductive particles, especially carbon particles, is supplied to the cathode and anode cells. During operation, when a voltage is applied through the electrodes, the conductive particles in the cathode cell acquire a negative charge, thereby adsorbing sodium ions in the middle cell, and the carbon particles in the anode cell acquire a positive charge, thereby adsorbing hydroxide ions. Here, this process is controlled so that sodium bicarbonate is mainly formed in the middle cell.

[0073] The voltage is preferably adjusted so that gas generation does not occur at the electrodes, thereby avoiding the undesirable side reaction of water electrolysis. The surface charge of conductive particles, particularly carbon particles, is at least partially neutralized in the cathode cell by sodium ions moving from the central cell through a cation-selective film (capacitive charging).

[0074] Preferably, a slurry containing conductive particles from a cathode cell charged with sodium ions is combined with a slurry containing conductive particles charged with hydroxide ions, preferably outside of its arrangement.

[0075] This produces a sodium hydroxide solution, which is preferably used again in the first step after precipitating the conductive particles.

[0076] In another embodiment, the ion-selective membrane configuration is an electrodialysis configuration, and in particular comprises only cation-selective membranes.

[0077] In particular, electrodialysis can be used to deplete sodium ions. In contrast to membrane capacitive enrichment, which is preferably operated in such a way that electrolysis of water does not occur at the electrodes, in an electrodialysis setup, electrolysis of water preferably occurs at the edge electrodes, thereby producing hydrogen and oxygen.

[0078] In particular, the electrodialysis configuration includes multiple cation-selective membranes inserted between the anode and cathode, each membrane separating adjacent cells into which water and sodium carbonate are alternately introduced, thereby ensuring that cells in which sodium hydroxide is formed and cells in which sodium bicarbonate is formed alternately.

[0079] The anode cell and cathode cell (edge ​​cell having these electrodes) are preferably filled with an electrolyte, such as a sodium sulfate solution, to ensure good conductivity for electrolysis. To compensate for the loss of sodium ions in the anode cell and the accumulation of sodium ions in the cathode cell, anolite and catholite are preferably pumped and mixed continuously and periodically.

[0080] In contrast to conventional electrodialysis, in which cation-selective and anion-selective membranes are alternately present, this specification preferably uses only cation-selective membranes, thereby preventing carbonate ions from moving toward the anode.

[0081] The solid sodium bicarbonate obtained in step III may be temporarily stored, used directly as a product, or used as a starting product for, for example, the electrochemical reduction of carbonates. If free carbon dioxide is required, step 3 may be carried out.

[0082] In the third stage, the sodium bicarbonate produced in the second stage is decomposed by a known method at a temperature of less than 350°C, preferably less than 250°C, for example, 50-200°C, more preferably 90-200°C, releasing carbon dioxide. The sodium carbonate produced in the third stage can be redissolved and reused in the second stage.

[0083] In summary, a process is disclosed for recovering carbon dioxide from gases containing carbon dioxide, particularly air or exhaust gases, by absorption into sodium hydroxide and release of CO2 from the formed sodium bicarbonate, provided that step (a) follows procedure III, and is further described below: - As an absorbent, a sodium hydroxide solution is brought into contact with a gas containing carbon dioxide, where sodium carbonate is formed, which preferably precipitates due to an excess solubility product and is preferably recovered in solid form by sedimentation, filtration, or centrifugation, preferably by filtration or centrifugation; - And, preferably, the obtained sodium carbonate is supplied to an electrochemical apparatus, where, in an electric field, sodium ions are depleted, preferably to 50% by weight, through an ion-selective membrane. This separates sodium bicarbonate from sodium hydroxide, both of which are obtained from the disproportionation of sodium carbonate; - And the sodium hydroxide obtained in the electrochemical apparatus is preferably returned to the first step of step (a). The concentration of the sodium hydroxide solution may be increased before recycling; - And, preferably, the dried sodium bicarbonate is used directly as a product or is thermally decomposed, in which carbon dioxide is released at high concentrations as a process product; - And, preferably, the sodium carbonate produced from the thermal decomposition is returned to the electrochemical apparatus to be disproportionated to sodium hydroxide and sodium bicarbonate.

[0084] In step (b), at least a portion of the recovered carbon dioxide is converted into an intermediate product containing an olefin.

[0085] Optionally, the intermediate product thus obtained may be subjected to a separation step to separate olefins and / or other substances contained in the intermediate product, such as by-products. Suitable separation processes, such as (fractional) distillation, filtration, membrane separation processes, precipitation, chromatography, extraction, stripping, gas-liquid separation, and the like, are known to those skilled in the art.

[0086] In a preferred embodiment, step (b) is carried out according to option (i), which involves electrochemically reducing carbon dioxide in the presence of water, thereby obtaining a mixture containing ethylene.

[0087] In particular, electrochemical reduction is carried out using renewable energy, especially electrical energy generated by photovoltaic and / or wind power units.

[0088] In particular, the mixture containing ethylene further comprises at least one compound selected from oxygen, formic acid, formate, carbon monoxide, hydrogen, methane, and / or lower alcohols. In particular, the formate is sodium formate. These byproducts are usually produced in the electrochemical reduction of carbon dioxide. The proportion of byproducts can be reduced by using special reaction conditions. However, in the method of the present invention, this is not a necessary condition for enabling the electrochemical reduction to be carried out with high efficiency.

[0089] The climate-active methane produced as a byproduct can be further converted into carbon (C) by recovering hydrogen gas (H2), thereby producing carbon that can be stored for long periods. As a result, the entire process not only produces ethylene components in a CO2-neutral manner, but also results in CO2 overcompensation.

[0090] Therefore, in a more preferred embodiment, the methane contained in the ethylene-containing mixture is decomposed into carbon and hydrogen.

[0091] Similarly, formic acid and / or formate salts are preferably decomposed into carbon monoxide and hydrogen, particularly by thermal decomposition.

[0092] Particularly preferred is the reaction of hydrogen and carbon monoxide to methanol, wherein carbon monoxide is obtained directly from a mixture containing ethylene and / or from the decomposition of formic acid and / or formate, and / or hydrogen is obtained directly from a mixture containing ethylene and / or from the decomposition of methane.

[0093] The reaction between hydrogen and carbon monoxide is carried out using a catalyst, particularly a Cu-based catalyst, and especially a Cu / ZnO / Al2O3 catalyst.

[0094] Therefore, formic acid, formate salts, hydrogen, and carbon monoxide can be converted to CO2-negative methanol. The methanol thus obtained can be used as a raw material and / or converted to olefins, for example, as described in step (b)(ii). In this way, all ethylene, and even all by-products in ethylene-containing mixtures, can be recycled and converted into less problematic substances and / or used for further applications.

[0095] The reactions and conditions necessary to carry out the above-mentioned reactions are themselves known to those skilled in the art.

[0096] According to a further preferred embodiment, step (b) is carried out according to option (ii). In particular, the hydrogenation of carbon dioxide and the subsequent conversion to olefins is carried out using renewable energy, in particular energy generated by photovoltaic units, wind turbines, and / or solar thermal collectors.

[0097] Therefore, carbon dioxide is preferably subjected to a catalytic hydrogenation reaction, where preferably a Cu-based catalyst and / or an In2O3-based catalyst, particularly Cu / ZnO / Al2O3, is used. In particular, the reaction temperature is selected from 150 to 350°C and / or the pressure during the reaction is 0.1 to 10 MPa.

[0098] In particular, step (b) is carried out according to option (ii), and the resulting methanol is converted to olefins, especially ethylene and / or propylene, in a methanol-olefin reaction (MTO) using a zeolite catalyst, especially aluminum silicon phosphate zeolite catalyst (silicoaluminophosphate zeolite catalyst). A particularly preferred reaction temperature is in the range of 250 to 550°C.

[0099] The methanol-olefin reaction is a petrochemical process. The process and suitable reaction conditions are known in themselves in the field of petrochemicals. Thereafter, a mixture of ethylene and propylene is formed from methanol via the intermediate dimethyl ether, particularly on an aluminum silicon phosphate zeolite catalyst. The olefin ratio of propylene (C3) to ethylene (C2) can be changed by selecting process conditions, for example, within the range of 0.77 in the ethylene mode to 1.33 in the propylene mode.

[0100] In another preferred embodiment, step (b) is carried out according to option (ii), and the resulting methanol is converted to olefins, particularly ethylene and / or propylene, in a methanol-gasoline reaction (MTG) using an aluminosilicate catalyst, such as ZSM-5.

[0101] If step (b) is carried out according to option (ii), optionally, steam crackling may be performed after the methanol-gasoline (MTG) reaction. In particular, steam crackling may be carried out using a silico-alumino-phosphate molecular sieve catalyst.

[0102] The methanol-gasoline reaction is a petrochemical process. The process itself and the appropriate reaction conditions are well known in the field of petrochemicals. The methanol-gasoline reaction is also known as the Mobil process. Typically, the reaction temperature is approximately 400°C.

[0103] Steam cracking is a petrochemical process in which saturated hydrocarbons are broken down into smaller, often unsaturated, hydrocarbons. It is a stable method for producing olefins such as ethylene and / or propylene.

[0104] In particular, optional step (c) is carried out. Thereafter, preferably, an olefin derivative is produced from the intermediate olefin, especially from ethylene and / or propylene. Examples of such derivatives are vinyl chloride, vinyl acetate, styrene, ethylene oxide, propylene oxide, monoethylene glycol, propylene glycol, acrylic acid, acrylic acid ester, and / or acrylonitrile.

[0105] Derivatization is a technique used in chemistry that converts a chemical compound into a derivative, which is a product with a similar chemical structure (a derivative of the reaction). Generally, specific functional groups of the compound being derivatized are involved in the derivatization reaction, and the chemical compound is converted into a derivative in which its reactivity, solubility, boiling point, melting point, aggregation state, and / or chemical composition are deviated.

[0106] Derivatization reactions for obtaining the aforementioned derivatives are known to those skilled in the art. These include, for example, oxidation reactions, halogenation reactions, hydrohalogenation reactions, alkylation reactions, and ammoxidation reactions.

[0107] In any step (c), particularly preferably, the ethylene obtained in step (b) is reacted with oxygen to obtain ethylene oxide. The ethylene oxide thus obtained can then be reacted, particularly hydrolyzed, to monoethylene glycol (MEG). The MEG thus obtained may be CO2 negative. In particular, MEG can be used as a raw material for the manufacture of further chemical products.

[0108] In another preferred embodiment, in step (c), the propylene obtained in step (b) is subjected to an ammoxidation reaction to form a nitrile, particularly acrylonitrile. The nitrile thus obtained may also be CO2 negative.

[0109] Therefore, by the method of the present invention, widely used chemical raw materials such as olefins, particularly ethylene and / or propylene, and even methanol and glycol, can be obtained from carbon dioxide.

[0110] In a very preferred embodiment, in step (d), the obtained glycol, particularly monoethylene glycol, is polymerized with terephthalic acid or 2,5-franzicarboxylic acid to obtain polyethylene terephthalate (PET) or polyethylene furanoate (PEF) as a polymer product. Suitable polymerization initiators, chain transfer agents, and polymerization conditions are known to those skilled in the art.

[0111] In this regard, 2,5-franzicarboxylic acid is obtained from biomass, preferably from fructose, and especially via the intermediate compound 5-hydroxymethylfurfural.

[0112] Similarly, in the method of the present invention, the substances and / or monomers used in particular in step (c) and / or step (d) are preferably at least partially, and especially entirely, bio-based substances and / or monomers.

[0113] Compounds from biomass are present in measurable proportions. 14 It contains the 1C isotope.14 By identifying the C content, it is possible to clearly demonstrate whether a compound, such as 2,5-franzicarboxylic acid, is biobased and the proportion of biobased compounds. Therefore, biobased compounds are 14 Compounds produced from fossil raw materials are not bio-based, but rather have a measurable proportion of carbon isotopes. 14 It does not contain C. 14 The C content and biobased content can be determined in accordance with ASTM D6866, "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis."

[0114] When appropriate conditions are selected, more CO2 is removed from the atmosphere during the manufacturing of raw materials in processes (a) to (c) than is released during combustion after the lifespan of the polymer product. This fact also applies to polymer products (e.g., PET or PEF) and consumer products made from them, such as bottles. Therefore, these polymer products can be manufactured to be CO2 negative.

[0115] In another preferred embodiment, in step (d), the olefin and / or glycol are converted to polyethylene glycol (PEG), polypropylene (PP), and / or polyethylene (PE). Suitable polymerization initiators, chain transfer agents, and polymerization conditions are known to those skilled in the art. As described above for PEG and PEF, these polymer products can also be manufactured to be CO2 negative.

[0116] In another preferred embodiment, in step (c), acrylonitrile is produced, particularly by the Sohio process, and subsequently polymerized in step (d) to form polyacrylonitrile. Similarly, this polymer can also be produced to be CO2 negative.

[0117] In another preferred embodiment, polyacrylonitrile is subjected to a thermal decomposition reaction to form carbon fibers. In particular, the carbon fibers can be combined with other materials, such as polymer products obtained by the method of the present invention, to form composite materials or carbon fiber-reinforced polymers.

[0118] Carbon fiber is widely used in the aerospace, automotive, and / or civil engineering industries. The ability to produce CO2-negative carbon fiber, composite materials, or carbon fiber-reinforced polymers is highly beneficial because it reduces the carbon footprint of carbon fiber-containing products.

[0119] In particular, carbon fibers, especially in the form of composite materials or carbon fiber-reinforced polymers, can be mixed with processable building materials, especially processable mortar or concrete materials, to produce building elements for buildings and / or infrastructure. Building elements include, for example, foundations, supports, beams, walls, floors, and / or ceilings.

[0120] Processable building materials include, in particular, binders, aggregates, and water. The binder may be selected from cement and / or other binder materials, such as geopolymers.

[0121] In particular, processable building materials contain geopolymer binders, especially as the sole binder. Such building materials are highly beneficial in terms of CO2 balance. Furthermore, when using this type of binder, the use of carbon fiber as a reinforcing element is highly beneficial, as metal reinforcements pose problems due to their lower pH. The combination of geopolymer binders and carbon fiber manufactured according to the method of this invention is highly advantageous in terms of CO2 balance.

[0122] In a further preferred embodiment, the method of the present invention further includes a step of obtaining hydrogen and / or oxygen by hydrolysis of water. In particular, the hydrogen and / or oxygen thus obtained are then used in step (b)(ii) and / or step (c).

[0123] In particular, hydrolysis is carried out using renewable energy, especially electrical energy generated by solar power units and / or wind power units.

[0124] Further aspects of the present invention relate to building elements that can be obtained by the methods described above. In particular, building elements include, for example, foundations, supports, beams, walls, floors, and / or ceilings of buildings or infrastructure.

[0125] Another embodiment, particularly relating to an apparatus for carrying out the above-described method, in particular a chemical plant, comprises the following: (a) Recovery units, particularly sorbent units, configured to recover carbon dioxide from gases containing carbon dioxide, especially from air or exhaust gases, especially by direct air recovery; (b) A conversion unit configured to convert at least a portion of the carbon dioxide recovered using the recovery unit into intermediate products comprising olefins, particularly ethylene and / or propylene, Here, the conversion unit preferably includes the following: - A reduction unit for electrochemically reducing carbon dioxide in the presence of water; and / or - A hydrogenation unit for hydrogenating carbon dioxide with hydrogen to form methanol, and then converting that methanol into olefins; (c) Optionally, a derivatization unit configured to derivatize at least a portion of the intermediate olefin to an olefin derivative; (d) A polymerization unit for polymerizing olefins and / or olefin derivatives, particularly together with at least one further monomer, to obtain a polymer product.

[0126] In another preferred embodiment, the apparatus further comprises at least one unit selected from the following: - Decomposition unit for decomposing formic acid and / or formate into carbon monoxide and hydrogen, - A decomposition unit that decomposes methane into carbon and hydrogen, and - Synthesis unit that converts hydrogen and carbon monoxide to methanol. - A hydrolysis unit for producing hydrogen and / or oxygen from water.

[0127] Optionally, the apparatus may further include a carbonation unit for generating carbon (C) from recovered carbon dioxide and hydrogen.

[0128] In particular, carbonation may be carried out via a Bosch reaction, which is especially preferably a two-step reaction involving quantitative water removal in the presence of an iron, cobalt, and / or nickel catalyst.

[0129] In addition, the plant preferably includes energy units configured to generate renewable energy, particularly photovoltaic units, wind power units, and / or solar thermal units, to generate the energy necessary to carry out one or more method processes. In particular, the energy units supply energy in the form of electricity and / or heat.

[0130] In particular, the apparatus is configured to recover at least 200,000 tons of CO2 per year, preferably at least 500,000 tons of CO2 per year.

[0131] According to a very preferred embodiment, the apparatus is part of a plant, particularly part of a chemical plant. However, individual units of the apparatus may be located in different locations. In this case, the chemical plant is a decentralized chemical plant.

[0132] Another aspect of the present invention relates to a combined power plant and chemical plant for reducing the carbon dioxide content in the atmosphere, particularly in the atmosphere and proportionally in water, preferably seawater, and for the production of polymer products.

[0133] In particular, the combined power plant and chemical plant shall include the following: - At least one electrolysis unit for oxygen production, comprising a certain amount of water (M H2O It is connected to at least one water supply line to receive the amount of water absorbed (M H2O ) is supplied, and the electrolyte is converted into a partial oxygen fraction (M) by electrolysis. O2 An electrolysis unit configured to produce a partial hydrogen fraction; - A conversion unit, preferably comprising the above-described unit, configured to convert at least a portion of the carbon dioxide recovered using a carbon dioxide sorbent unit into intermediate products comprising olefins, particularly ethylene and / or propylene: - A reduction unit for electrochemically reducing carbon dioxide in the presence of water; and / or - A hydrogenation unit for hydrogenating carbon dioxide with hydrogen to form methanol, and then converting that methanol into olefins; - Optionally, at least one derivatization unit for derivatizing at least a portion of the intermediate olefin to an olefin derivative; - At least one polymerization unit for polymerizing olefins and / or olefin derivatives, particularly together with at least one further monomer, to obtain a polymer product; - At least one hydrogen transport device for connecting an electrolysis unit to a carbonation unit for carbon synthesis, and preferably further connecting the electrolysis unit to a conversion unit, and in particular to the hydrogenation unit of the conversion unit; - A carbon dioxide sorption unit configured to purify ambient air of the external atmosphere surrounding the unit, in particular at least one carbon dioxide sorption unit as described above, having at least one air inlet for supplying ambient air and at least one downstream sorbent device configured to extract a certain amount of carbon dioxide from the ambient air, as described above in particular; and - At least one carbon dioxide transport means connecting the carbon dioxide sorption unit to a carbonation unit and a conversion unit; Here,[[]]END]] - The electrolysis unit has at least one oxygen outlet for discharging an oxygen fraction (M O2 ), the carbon dioxide sorption unit has at least one air outlet for discharging the purified ambient air, the oxygen outlet and the air outlet open to the external atmosphere, the carbonation unit has a carbon outlet for carbon removal, and - At least one power generation unit is provided for the self-power supply source of the plant, which is for generating power from one or more energy sources, in particular a power generation unit for generating power using only renewable energy sources exclusively for power generation.

[0134] In particular, further features of the plant may be implemented in accordance with the specification of German Patent No. 10 2021 104 746 B3, which is incorporated herein by reference.

[0135] In the plant described above, the units are configured to implement the method of the present invention. Here, in particular, the carbon dioxide sorption (absorption) unit and the sorbent unit are connected to a solar heat source and / or a waste heat source.

[0136] Other advantageous embodiments and combinations of features will become apparent from the following detailed description and the entire claims.

[0137] The drawings used in the description of the embodiments show the following.

Brief Description of the Drawings

[0138] [Figure 1] Figure 1 is a flowchart of the present invention's method for producing polymer products. [Figure 2] Figure 2 is a flowchart illustrating the implementation of the first step 1 of the method shown in Figure 1, in which carbon dioxide is recovered directly from the gas containing carbon dioxide using sodium hydroxide. [Figure 3] Figure 3 is a schematic diagram of the membrane capacitive process for disproportionation of sodium carbonate in the method shown in Figure 2. [Figure 4] Figure 4 is a flowchart illustrating the implementation of the method shown in Figure 1 for producing polyethylene terephthalate and polyethylene furanoate. [Figure 5] Figure 5 is a flowchart showing a further implementation of the method in Figure 4, in which additional intermediate products are used in addition to polyethylene terephthalate and polyethylene furanoate. [Figure 6] Figure 6 is a flow chart showing the manufacturing process of carbon fibers or carbon fiber-reinforced polymers. [Modes for carrying out the invention]

[0139] In the diagram, identical components are assigned the same reference numeral.

[0140] Figure 1 shows a flow chart of the method of the present invention for producing polymer products. Specifically, in recovery unit 1 (carrying out step (a) of the present invention), carbon dioxide is recovered from a gas containing carbon dioxide, particularly air or exhaust gas. The carbon dioxide thus obtained is then subjected to conversion units 2(i) and / or 2(ii) (carrying out step (b) of the present invention). In unit 2(i), at least a portion of the recovered carbon dioxide is electrochemically reduced in the presence of water to obtain an intermediate product containing olefins, particularly ethylene and / or propylene. In unit 2(ii), carbon dioxide is first hydrogenated with hydrogen to form methanol. Subsequently, this methanol is subjected to a methanol-olefin reaction, MTO (methanol-to-olefin reaction) and / or a methanol-gasoline reaction, MTG (methanol-to-gasoline reaction) to obtain an intermediate product containing olefins, particularly ethylene and / or propylene.

[0141] In a derivatization unit 3 (which carries out any step (c) of the present invention) as desired, the olefin can be subjected to a derivatization reaction to obtain an olefin derivative, such as glycol and / or acrylonitrile. Depending on the derivatization reaction, reactants such as oxygen, water and / or ammonia are supplied.

[0142] Subsequently, the olefin and / or olefin derivative, together with at least one further monomer if desired, are subjected to polymerization unit 4 to obtain a polymer product (carrying out step (d) of the present invention).

[0143] The hydrogen used in unit 2(ii) and the oxygen suitable for derivatization unit 3 can be generated from water in hydrolysis unit 1a, which may be present as desired.

[0144] Figure 2 is a flowchart showing the process in Unit 1 of the method shown in Figure 1, in which carbon dioxide is recovered directly from the gas containing carbon dioxide using sodium hydroxide.

[0145] In the first step 11.1, a gas containing carbon dioxide (CO2) is brought into contact with sodium hydroxide (NaOH), for example, a sodium hydroxide solution and / or solid sodium hydroxide, to absorb the carbon dioxide. Sodium carbonate (Na2CO3) is formed during the process of step 11.1. Depending on the specific implementation of step 11.2, the sodium carbonate is supplied as a solid (step I) or in the form of an aqueous solution (steps II and III).

[0146] In the second step 11.2, gaseous carbon dioxide and a dilute sodium hydroxide solution, particularly a sodium hydroxide solution, are formed from the sodium carbonate obtained in the first step (a) and / or from sodium bicarbonate converted from the sodium carbonate obtained in the first step (a) at a temperature of less than 350°C, preferably less than 250°C, for example, 50 to 200°C, more preferably 90 to 200°C. Here, step 11.2 can be carried out according to at least one of procedures I, II, and / or III.

[0147] In procedure I, the sodium carbonate obtained in step 11.1 is used in a solid state and is thermally decomposed at least partially at a temperature of, for example, 90°C to 200°C, thereby releasing gaseous carbon dioxide. The further sodium hydroxide obtained by thermal decomposition is extracted with an extractant, for example, water or an aqueous alcohol solution, particularly in parallel with the thermal decomposition of sodium carbonate.

[0148] In procedure II, the sodium carbonate obtained in step 11.1 is used in the form of an aqueous solution, and this aqueous solution is heated, in particular to a temperature below the boiling point of the aqueous solution, to at least partially decompose the sodium carbonate, thereby releasing gaseous carbon dioxide from the solution.

[0149] In step III, the sodium carbonate obtained in step 11.1 is used in aqueous solution form and separated at least partially into sodium bicarbonate and sodium hydroxide by an ion-selective membrane configuration. In this third step, the obtained sodium bicarbonate is at least partially thermally decomposed to obtain carbon dioxide and sodium carbonate. Figure 3 shows an exemplary embodiment of the ion-selective membrane configuration.

[0150] Figure 3 shows a schematic diagram of a membrane capacitive configuration and process for sodium carbonate disproportionation that can be used in Procedure III. Here, a concentrated sodium carbonate solution (Na2CO3 in water) is introduced into the center cell D at one end and pumped countercurrently to the slurry of conductive activated carbon particles flowing through the cathode cell B and anode cell F. The center cell D is closed by two cation-selective membranes C and E. Sodium ions move through membrane C to the cathode cell B, and protons from the anode cell F move through membrane E to the center cell D. The cathode cell B is closed on the outside by an edge electrode A made of a conductive material such as carbon or stainless steel, which is conductively connected to the negative electrode of a current source (not shown). The anode cell F has an edge electrode G conductively connected to the positive electrode of an external current source as its outer boundary. The slurry of conductive activated carbon is pumped countercurrently to the center cell D through the anode and cathode cells B and F.

[0151] The charge of the activated carbon particles added via edge electrode A is neutralized in cathode cell B by sodium ions moving from center cell D through cation-selective membrane C. In anode cell F, the positive charge of the activated carbon particles added by edge electrode G is offset by hydroxide ions from the dissociation of water. The protons released in this process move through the cation-selective membrane E to middle cell D in the electric field.

[0152] After passing through cathode cell B or anode cell F, the carbon slurries from the two cells are combined outside the cell, and after the electric field is removed, sodium hydroxide is formed by a neutralization reaction. The carbon particles are discharged in this process. The discharged carbon particles I are separated from the caustic soda H by filtration or sedimentation, and the carbon particles I are made into a slurry with fresh water and returned to cells B and F. The caustic soda H is added to the absorption unit in step 11.1 of the method.

[0153] Figure 4 shows a flowchart illustrating the implementation of the method shown in Figure 1 for producing polyethylene terephthalate and polyethylene furanoate.

[0154] As explained in Figure 1, the recovered carbon dioxide is subjected to an electrochemical reduction step 12.1 in the presence of water to obtain an intermediate product mixture. Next, this product mixture is subjected to a separation step 12.2 to isolate the ethylene contained in the intermediate product mixture. Steps 12.1 and 12.2 are specific implementations of the conversion step 2(i) shown in Figure 1.

[0155] Next, the ethylene thus obtained is subjected to oxidation step 13.1 to produce ethylene oxide, which is then treated with water in hydrolysis step 13.2 to produce monoethylene glycol as an ethylene derivative. Steps 13.1 and 13.2 are specific implementations of the arbitrary derivatization step 3 in Figure 1.

[0156] Subsequently, in polymerization step 14.1, monoethylene glycol is polymerized together with terephthalic acid to produce polyethylene terephthalate (PET), and / or in polymerization step 14.2, monoethylene glycol is polymerized together with 2,5-franzicarboxylic acid to produce polyethylene furanoate (PEF). Steps 14.1 and 14.2 are specific implementations of polymerization step 4, which is performed as desired in Figure 1.

[0157] Figure 5 is a flowchart illustrating a further implementation of the method in Figure 4, in which all by-products in the mixture, including ethylene and even recycled ethylene, in addition to PET and PEF, are converted into less problematic substances or used in further applications.

[0158] Specifically, as explained in Figure 1, the recovered carbon dioxide is subjected to an electrochemical reduction step 12.1 in the presence of water to obtain an intermediate product mixture. Next, this product mixture is subjected to a separation step 12.2 to isolate ethylene, oxygen, formate, formic acid, carbon monoxide (CO), hydrogen, methane, and alcohol contained in the intermediate product mixture. Appropriate methods for separating and isolating these substances are known to those skilled in the art.

[0159] The separated ethylene is subjected to the same process as described in Figure 4 to produce PET and / or PEF.

[0160] Oxygen may be used in the derivatization of ethylene in step 13.1 and / or for other purposes.

[0161] The formate, which exists as sodium formate, can be decomposed, particularly by thermal decomposition step 16, by heating above 300°C, with the removal of hydrogen and monoxide (1:1), leaving Na2CO3. Depending on the temperature and type of catalyst used, formic acid can be decomposed in step 16 into carbon dioxide and hydrogen, and / or carbon monoxide and water. Both reactions are equilibrium reactions.

[0162] The products of the pyrolysis step 16, as well as the further carbon monoxide and hydrogen separated from the intermediate product mixture, can be reacted in the hydrogenation step 17 to produce methanol.

[0163] Similarly, methane separated from the intermediate product mixture can be decomposed into hydrogen and carbon (C) in decomposition step 18. The carbon can be stored and thereby removed from the atmosphere over the long term. The hydrogen obtained in this process may be reused in hydrogenation step 17 or used for other purposes.

[0164] The alcohols contained in the intermediate product mixture are used, for example, in the chemical industry.

[0165] In the method shown in Figure 5, all components in the intermediate product mixture may be used as is, or / or converted into other useful substances.

[0166] However, the present invention is not limited to the examples shown in the specific embodiments. For example, other polymer materials, such as polyethylene, polypropylene, polystyrene, polyacrylonitrile, and many further polymer materials, can be produced instead of PET and PEF.

[0167] Furthermore, polymer materials produced by the method of the present invention may be converted into other products. For example, polyacrylonitrile can be converted into carbon fibers, which can be used as reinforcing materials for building materials and / or in industrial applications.

[0168] Figure 6 shows a flow chart illustrating the production of carbon fibers or carbon fiber-reinforced polymers. Here, the propylene obtained in conversion unit 2(i) or 2(ii) (see Figure 1) is converted to acrylonitrile in derivatization unit 3 using ammonia. Subsequently, the acrylonitrile is subjected to a polymerization reaction in polymerization unit 4 to form polyacrylonitrile.

[0169] In a further step, the polyacrylonitrile is decomposed in the pyrolysis unit 5 to form carbon fibers. Optionally, these carbon fibers can be embedded in a polymer material (which may also be manufactured by the method of the present invention or not) to form a carbon fiber-reinforced polymer.

[0170] The carbon fibers or carbon fiber-reinforced polymers obtained in this way can be used, for example, in the aerospace, automotive, and / or civil engineering industries as reinforcing materials for building materials such as mortar or concrete structures.

[0171] These carbon fibers and carbon fiber-reinforced polymers can be manufactured in a CO2-negative manner. This allows for a reduction in the carbon footprint of products containing these components.

Claims

1. A carbon-negative method for producing polymer products, comprising the following steps: (a) Recovering carbon dioxide from gases containing carbon dioxide, especially from air or exhaust gases, especially by direct air recovery (1, 11.1, 11.2); (b) Converting at least a portion of the recovered carbon dioxide into an intermediate product comprising an olefin, particularly ethylene and / or propylene, preferably by the following means (2, 12.1): (i) electrochemically reducing the carbon dioxide in the presence of water (2i, 12.1); and / or (ii) Hydrogenating the carbon dioxide with hydrogen to form (2ii) methanol, and then converting the methanol to the olefin, preferably by the following: - Methanol-olefin reaction (MTO); and / or - Methanol-gasoline reaction (MTG); (c) Optionally, the olefin of the intermediate product is subjected to a derivatization reaction (3, 13.1, 13.2) to obtain an olefin derivative, particularly glycol and / or acrylonitrile; (d) Further polymerization of the olefin and / or olefin derivative, particularly together with at least one further monomer (4, 14.1, 14.2) to obtain a polymer product; Here, in at least step (a), particularly in at least steps (a) and (b), and particularly in all steps (a) to (d), the energy required to carry out the steps of this method is supplied in the form of renewable energy. method.

2. The method according to claim 1, further comprising the step of generating the renewable energy using a photovoltaic unit and / or a wind power unit and / or a solar thermal collector, wherein the energy is generated in a plant where step (a), particularly steps (a) and (b), or all of the steps are carried out.

3. In step (a) of the method, In the first stage, the gas containing carbon dioxide is brought into contact with sodium hydroxide, particularly a sodium hydroxide solution and / or solid sodium hydroxide, to absorb carbon dioxide and form sodium carbonate, and The method according to claim 1 or 2, wherein in the second step, gaseous carbon dioxide and a solution of sodium hydroxide, particularly sodium hydroxide, are formed from the sodium carbonate obtained in the first step and / or sodium bicarbonate converted from the sodium carbonate obtained in the first step at a temperature of less than 350°C, preferably less than 250°C, for example 50 to 200°C, more preferably 90 to 200°C.

4. The method according to any one of claims 1 to 3, wherein step (b) is carried out by option (i) to obtain a mixture comprising ethylene and at least one compound selected from oxygen, formic acid, formate, carbon monoxide, hydrogen, methane, and / or lower alcohols.

5. The method according to claim 4, wherein the formic acid and / or formate salt is decomposed into carbon monoxide and hydrogen.

6. The method according to claim 4 or 5, wherein the methane is decomposed into carbon and hydrogen.

7. The hydrogen and carbon monoxide are reacted to produce methanol. The carbon monoxide is obtained directly from the mixture containing ethylene and / or from the decomposition of formic acid and / or formate, and / or The hydrogen is obtained directly from the mixture containing ethylene and / or from the decomposition of methane. The method according to any one of claims 4 to 6.

8. Step (b) is carried out according to option (ii), and the carbon dioxide is subjected to a catalytic hydrogenation reaction to obtain methanol, where a Cu-based catalyst and / or In ２ O ３ Catalyst systems, especially Cu / ZnO / Al ２ O ３ The method according to any one of claims 1 to 7, using

9. The method according to any one of claims 1 to 8, wherein step (b) is carried out by option (ii), and in a methanol-olefin reaction using a zeolite catalyst, particularly an aluminum silicon phosphate zeolite catalyst, the methanol obtained is converted to the olefin, particularly ethylene and / or propylene.

10. The method according to any one of claims 1 to 9, wherein step (b) is carried out by option (ii), and in a methanol-gasoline reaction using an aluminosilicate catalyst, for example ZSM-5, the obtained methanol is converted to the olefin, particularly ethylene and / or propylene.

11. The method according to any one of claims 1 to 10, wherein in step (c), the ethylene obtained in step (b) is reacted with oxygen to obtain ethylene oxide, and the ethylene oxide thus obtained is reacted to produce monoethylene glycol.

12. The method according to any one of claims 1 to 11, wherein in step (c), the propylene obtained in step (b) is subjected to an ammoxidation reaction to form a nitrile, particularly acrylonitrile.

13. The method according to any one of claims 1 to 12, wherein in step (d), the obtained glycol, particularly monoethylene glycol, is polymerized with terephthalic acid or 2,5-franzicarboxylic acid to obtain polyethylene terephthalate (PET) or polyethylene furanoate (PEF) as the polymer product.

14. The method according to claim 13, wherein the 2,5-franzicarboxylic acid is obtained from biomass, preferably from fructose, and particularly via the intermediate compound 5-hydroxymethylfurfural.

15. The method according to any one of claims 1 to 14, wherein in step (d), the olefin and / or the glycol is converted to polyethylene glycol (PEG), polypropylene (PP), and / or polyethylene (PE).

16. The method according to any one of claims 12 to 15, wherein the acrylonitrile is polymerized to form polyacrylonitrile.

17. The method according to claim 16, wherein the polyacrylonitrile is subjected to a thermal decomposition reaction to form carbon fibers.

18. The method according to claim 17, wherein the carbon fibers are mixed with a processable building material, particularly in the form of a composite material and / or a carbon fiber reinforced polymer, and particularly with a processable mortar or concrete material, to produce building elements for buildings and / or infrastructure, such as foundations, supports, beams, walls, floors and / or ceilings.

19. The method according to claim 18, wherein the processable building material comprises a geopolymer binder.

20. A building element obtained by the method described in claim 18 or 19.

21. Apparatus for carrying out the method described in any one of claims 1 to 19, particularly a chemical plant, comprising: (a) Recovery unit (1), in particular carbon dioxide sorbent unit, configured to recover carbon dioxide from gases containing carbon dioxide, in particular from air or exhaust gases, in particular by direct air recovery; (b) A conversion unit (2) configured to convert at least a portion of the carbon dioxide recovered using the recovery unit into an intermediate product comprising an olefin, particularly ethylene and / or propylene. Here, the conversion unit preferably comprises the following: - A reduction unit (2i) for electrochemically reducing carbon dioxide in the presence of water; and / or - A hydrogenation unit (2ii) for hydrogenating the carbon dioxide with hydrogen to form methanol, and subsequently converting the methanol into the olefin; (c) Optionally, a derivatization unit (3) configured to derivatize at least a portion of the olefin of the intermediate product into an olefin derivative; (d) A polymerization unit (4) for polymerizing the olefin and / or olefin derivative, particularly together with at least one further monomer, to obtain a polymer product.

22. The apparatus according to claim 21, further comprising an energy unit configured to generate renewable energy, in particular a photovoltaic unit, a solar thermal unit, and / or a wind energy unit.

23. The apparatus according to claim 21 or 22, further comprising at least one unit selected from the following: - Separation unit (12.2) capable of separating by-products, in particular at least one compound selected from oxygen, formic acid, formate, carbon monoxide, hydrogen, methane, and / or lower alcohols, from the intermediate product containing the olefin; - Decomposition unit (16) for decomposing formic acid and / or formate into carbon monoxide and hydrogen; - Decomposition unit (18) for decomposing methane into carbon and hydrogen; and - Synthesis unit (17) that converts hydrogen and carbon monoxide into methanol.

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