Sustainable production of organic amino compounds for production of organic isocyanates

Abstract

The invention relates to a method according to claim 1, in which nitric acid, as a direct process product of a nitric acid production process, comprising the following steps: a) providing hydrogen (5d) and oxygen (5b) by electrolysis (5) of water in an electrolysis unit, in which electricity (10) from renewable energy sources and water (5c) are used; b) providing ammonia (21b) as a process product of the reaction of at least nitrogen (21a) and hydrogen (5d) from the electrolysis (5) of said water in the ammonia synthesis (21); c) producing nitric acid (22) by reacting previously provided ammonia (21b) with at least an oxygen-containing gas (5e) in a nitric acid production (22), used for the production 22 of organic amino compounds (17) for the synthesis of organic isocyanate compounds. Also described herein are methods of incorporating the present methods into the preparation of organic isocyanate compounds from these organic amino compounds, and an apparatus for implementing the corresponding methods.

Description

[0001] The present invention relates to a method for the sustainable production of an organic amino compound for the synthesis of an organic isocyanate compound, wherein the organic amino compound is prepared using green hydrogen and green ammonia, as well as a method for producing an organic isocyanate compound using the organic amino compound and a device for carrying out the corresponding method.

[0002] Isocyanates are usually produced by reacting amines with phosgene, forming hydrogen chloride as a by-product. The carbon monoxide required for phosgene synthesis is obtained from a reforming process utilizing natural gas, wherein the chlorine used for phosgene synthesis is produced by recycling hydrogen chloride from isocyanate production or by chlor-alkali electrolysis.

[0003] The amines are produced by hydrogenation of nitro compounds which in turn are produced from nitric acid from corresponding precursors. Nitric acid is produced from ammonia, the hydrogen for its synthesis usually being provided by reforming processes.

[0004] The isocyanates are derived from phosgene and amines, which react with polyols and / or polyesters to give polyurethane materials.

[0005] Polyurethane, also referred to as PU in the following, is a plastic formed by the polyaddition reaction of a polyol containing at least two hydroxyl groups with a polyisocyanate. Polyisocyanates are referred to as isocyanates in the following, unless otherwise specified. Amines used to produce isocyanates are also polyamines and are referred to as amines. The use of diols and diisocyanates produces linear polyurethanes. Crosslinked polyurethanes can be obtained by reacting a triisocyanate-diisocyanate mixture with a triol-diol mixture. The properties of PU can vary within a wide range. Depending on the degree of crosslinking and / or the isocyanate or OH component used, thermosetting plastics, thermoplastics or elastomers can be obtained. However, polyurethanes are also used as molding materials for compression molding, such as casting resins (isocyanate resins), (textile) elastic fibers, polyurethane coatings and polyurethane adhesives. It is also easy to make foams from polyurethanes.

[0006] Flexible PU foams have many uses, especially as interior finishing materials, such as furniture and car seats, mattress foams, carpet backing materials, textile lamination, cleaning sponges or filter materials.

[0007] Rigid PU foam is mainly used for thermal insulation, such as buildings, cooling devices, cold and hot storage, and some piping systems (plastic sheathed composite pipes, flexible composite pipes).

[0008] Some other relatively new application areas of PU foams are in automotive construction such as soft coatings for steering wheels, armrests, handles, interior trim, dashboards, sound insulation, noise protection, sealing, clear coatings for wood trim.

[0009] It was an object of the present invention to find a more sustainable method for the synthesis of organic amino compounds for the production of isocyanates and ultimately for the production of polyurethanes, which can be used in existing polyurethane processes without any major additional complexity.

[0010] The "sustainability" of the process is understood by those skilled in the art according to the definition of sustainability (sustainable development) coined by the United Nations in the Brundtland Report of the "World Commission on Environment and Development", which means that the current process is carried out with as little or no impact as possible on the ability of future generations to meet their own needs, especially with regard to the use of resources such as mineral raw materials, and especially with regard to the protection of living space, such as the Earth's atmosphere. Therefore, the object of the present invention is to make the production of organic amines and the production of organic isocyanates, and the polyurethanes produced therefrom, more sustainable than the production methods known in the prior art. The impact of the production of isocyanates and polyurethanes on the reduction of the satisfaction of the needs of future generations should be reduced or avoided.

[0011] The present invention provides a method for producing an organic amino compound for synthesizing an organic isocyanate compound, comprising at least the following steps: i) providing at least one organic nitro compound as a process product for a synthesis process of at least one organic nitro compound, comprising at least the following steps:

[0012] i-1) providing nitric acid as a direct process product of a nitric acid production process, comprising at least the following steps:

[0013] a) providing hydrogen and oxygen by electrolysis of water in an electrolysis device using electricity from renewable energy sources and using water;

[0014] b) providing ammonia as a direct process product of the reaction of at least nitrogen and hydrogen from the electrolysis of said water in the synthesis of ammonia;

[0015] c) producing nitric acid by reacting previously produced ammonia at least with an oxygen-containing gas in the production of nitric acid;

[0016] i-2) synthesizing at least one organic nitro compound, preferably at least one aromatic organic nitro compound, by nitrating at least one organic compound, preferably at least one aromatic organic compound, with at least the nitric acid provided;

[0017] ii) providing hydrogen, preferably by electrolysis of water in an electrolysis device,

[0018] where electricity produced from renewable energy sources is used;

[0019] iii) introducing the provided at least one organic nitro compound and the provided hydrogen into a hydrogenation, and then reducing the nitro group of the at least one organic nitro compound by reaction with the hydrogen to obtain at least one organic amino compound, preferably at least one aromatic organic amino compound.

[0020] For the supply of the at least one organic nitro compound in step i), it is sufficient if the at least one organic nitro compound is a direct process product of at least one of the above-mentioned process steps i-1) and i-2). This means that for the performance of the step of providing the at least one organic nitro compound, it is sufficient to deliver the organic nitro compound as a direct process product from at least step i-1) and step i-2) simply as a raw material from a storage container or a feed port. In this case, the manufacturer of the organic amine produced by the process according to the invention does not itself perform the above-mentioned steps for producing the at least one organic nitro compound, but ensures that the organic nitro compound provided for the production of the organic amine is produced by using a process having at least steps i-1) and i-2) and is therefore a direct process product thereof.

[0021] In the case of transport, the method is preferably carried out in such a way that in step i), the organic nitro compound as a process product of the synthesis described in step i-2) is provided in a movable closed transport container and optionally transferred therefrom to a storage container for intermediate storage,

[0022] The synthesis described therein and the hydrogenation in step iii) are not fluidically connected to one another.

[0023] By fluid connection is meant a part of a device that connects other parts of the device together and can carry material in any state of matter from one part of the device to the next as a material flow, such as a feed in the form of a tube. The expression "fluid connection" means that designated parts of a device are in fluid connection with each other.

[0024] The movable closed transport container can be, for example, a tanker, a tank ship or a tank truck. The so-called "closed" means that during the transport process, the transport container is sealed at its device for loading or extracting the transported material.

[0025] According to the invention, a storage container is a container located at a fixed location, such as a tank farm. The storage container belongs to the fixed plant capacity or is part of it.

[0026] In one embodiment of the process according to the invention which is preferred according to the invention, the organic nitro compound is provided as a direct process product of the synthesis described in step i-2) in the form of a material stream directly via a fluid connection from the synthesis via intermediate storage (if necessary) in at least one storage container, wherein the synthesis, any necessary at least one storage container and the hydrogenation in step iii) are fluidically connected to one another. As a particularly preferred embodiment, the process in this preferred embodiment comprises at least the following steps

[0027] i) producing at least one organic nitro compound by at least the following steps:

[0028] i-1) providing nitric acid as a direct process product of a nitric acid production process, comprising at least the following steps:

[0029] a) Providing hydrogen and oxygen by electrolysis of water using water in an electrolysis device, wherein the electricity used comes from renewable energy sources;

[0030] b) providing ammonia as a direct process product of the reaction of at least nitrogen and hydrogen from the electrolysis of said water in the synthesis of ammonia;

[0031] c) providing nitric acid by reacting previously provided ammonia at least with an oxygen-containing gas in the production of nitric acid;

[0032] i-2) nitrating at least one organic compound, preferably at least one aromatic organic compound, by at least the nitric acid provided to synthesize at least one organic nitro compound, preferably at least one aromatic organic nitro compound;

[0033] ii) providing hydrogen, preferably by electrolysis of water in an electrolysis device,

[0034] where electricity generated from renewable energy sources is used;

[0035] iii) introducing the organic nitro compound and the provided hydrogen into a hydrogenation, and then hydrogenating the nitro group of the at least one organic nitro compound by reduction thereof by reaction with the hydrogen to obtain at least one organic amino compound, preferably at least one aromatic organic amino compound, with the proviso that the organic nitro compound is introduced as a material stream from the synthesis in step i-2) via a fluid connection, optionally via intermediate storage in at least one storage container, wherein the synthesis and the hydrogenation in step iii) and any at least one storage container are fluidically connected to each other.

[0036] The synthesis of at least one organic nitro compound in step i-2) is carried out from the organic compound and the nitric acid in a manner very familiar to the person skilled in the art. For example, organic mononitro compounds, in particular organic aromatic mononitro compounds, can be obtained by the synthesis in step i-2), as described in EP 0 668 263 A1, which is expressly incorporated herein in its entirety by reference. A preferred organic nitro compound is mononitrobenzene. In addition, organic dinitro compounds, such as dinitrotoluene (DNT), can be obtained by the synthesis in step i-2). The preparation of dinitrotoluene is very familiar to the person skilled in the art, for example from the following documents: Ullmann's der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 4th edition, volume 17, pages 391 et seq., 1979, Verlag Chemie Weinheim / New York; H. Hermann, J. Gebauer, P. Konieczny, "Industrial Nitration of Toluene to Dinitrotoluene" in ACS-Symposium, Series 623, 234-249, 1996, ed. LF Albright, RVC, or from EP 1 880 989 A1, which are expressly incorporated herein in their entirety by reference.

[0037] For the supply of the organic nitro compound in step ii), an organic compound (preferably at least one aromatic organic compound) is nitrated using at least the nitric acid provided. The organic compound used is more preferably selected from benzene and toluene.

[0038] In another embodiment, it has been found that the sustainability can be improved when the at least one organic compound used in step i-2) is an aromatic organic compound provided as a direct process product of a process comprising at least the following steps:

[0039] Pyrolyzing the organic material at a temperature of 600 to 1000°C to obtain a gaseous pyrolysis product and a pyrolysis residue;

[0040] contacting the gaseous pyrolysis product with a heterogeneous catalyst to obtain a conversion product containing at least one aromatic organic compound having a molecular weight of less than 300 g / mol;

[0041] The conversion product is processed to obtain said aromatic organic compound, in particular an aromatic organic compound selected from the group consisting of benzene, toluene and xylene.

[0042] For example, a corresponding pyrolysis process is described in WO 2020 / 204707 A1, which is expressly incorporated herein in its entirety by reference. The document also describes heterogeneous catalysts suitable for the process for producing conversion products.

[0043] The organic material used for pyrolysis can be, for example, plastics, such as polyurethane materials and / or polycarbonate materials. Such plastics are preferably plastic waste, such as polyurethane material waste. The "plastic waste", particularly "polyurethane material waste" may occur on the market by using plastics, particularly polyurethane. In the case of polyurethane material waste, the preferred polyurethane is produced in turn by the isocyanate produced from the organic amine provided by the method of the present invention. In the case of utilizing this polyurethane material waste in the process of the present invention, this is referred to as a "closed loop" process. However, in this embodiment of the method of the present invention, of course, polyurethane material waste of polyurethane that is not produced from the diisocyanate of the method of the present invention can also be utilized.

[0044] There is a further improvement in the corresponding pyrolysis process for providing aromatic organic compounds, in which the pyrolysis residue obtained by pyrolysis is converted into carbon monoxide, hydrogen and residue material by partial oxidation gasification, the carbon monoxide formed after optional processing is entered into the phosgene synthesis, and the hydrogen is introduced into the hydrogen supply of step ii) of the present method.

[0045] At least one organic nitro compound is synthesized in step i-2) from at least one organic compound and nitric acid. In step i-1) of the process and other embodiments of the present invention, nitric acid is provided for the synthesis in step i-2). For the supply of at least one organic nitro compound, it is sufficient if the nitric acid provided is a direct process product of at least one of steps i-1) a) to c) of the process in the preferred embodiment or general process of the present invention.

[0046] This means that, when carrying out the step of providing nitric acid, it is sufficient to simply deliver said nitric acid as a direct process product of a process having at least steps i-1) a) to i-1) c) from a storage container or a feed port. In this case, the manufacturer of the organic amine or organic nitro compound produced by the process according to the invention does not itself carry out the above-mentioned step of producing nitric acid, but only ensures that the nitric acid provided for the production of the organic amine or for the production of the organic nitro compound is produced at least by using steps i-1) a) to c) and is therefore a direct process product thereof. In the case of delivery, the method is preferably carried out in such a way that in step i-1) the nitric acid is provided as a direct process product of the nitric acid production into a movable closed transport container and optionally transferred therefrom to a storage container for intermediate storage, wherein the nitric acid production and the synthesis in step ii) are not fluidically connected.

[0047] Likewise, according to the invention, when providing nitric acid, at least one of the above-mentioned reaction steps for producing nitric acid is carried out as an integral step in the process for producing an organic amine according to the invention, and the nitric acid obtained in the process may also be sent to the synthesis of the organic nitro compound after optionally intermediate storage in a storage container. Here, it is preferred that in step i-1), nitric acid is provided as a process product of the nitric acid production in the form of a material flow directly via a fluid connection from the nitric acid production via intermediate storage (if necessary) in at least one storage container, wherein the nitric acid production, any necessary at least one storage container and the synthesis in step i-2) are fluidically connected to each other.

[0048] As a particularly preferred embodiment, the method in this preferred embodiment comprises at least the following steps i) producing at least one organic nitro compound by at least the following steps:

[0049] i-1) providing nitric acid as a direct process product of a nitric acid production process, comprising at least the following steps:

[0050] a) Providing hydrogen and oxygen by electrolysis of water using water in an electrolysis device, wherein the electricity used comes from renewable energy sources;

[0051] b) providing ammonia as a direct process product of the reaction of at least nitrogen and hydrogen from the electrolysis of said water in the synthesis of ammonia;

[0052] c) providing nitric acid by reacting previously provided ammonia at least with an oxygen-containing gas in the production of nitric acid;

[0053] i-2) synthesizing at least one organic nitro compound, preferably at least one aromatic organic nitro compound, by nitrating at least one organic compound, preferably at least one aromatic organic compound, with at least said nitric acid;

[0054] ii) providing hydrogen, preferably by electrolysis of water in an electrolysis device,

[0055] where electricity generated from renewable energy sources is used;

[0056] iii) introducing the provided organic nitro compound and the provided hydrogen into a hydrogenation, and then hydrogenating the nitro group of the at least one organic nitro compound by reduction thereof by reaction with the hydrogen to obtain at least one organic amino compound, preferably at least one aromatic organic amino compound, provided that firstly, in step i-1), nitric acid is provided as a direct process product of the nitric acid production in the form of a material flow directly from the nitric acid production via a fluid connection, via intermediate storage (if necessary), in at least one storage vessel, wherein the nitric acid production, any necessary at least one storage vessel and the synthesis in step ii) are fluidically connected to one another, and, secondly, the organic nitro compound is introduced in the form of a material flow from the synthesis in step i-2) via a fluid connection, optionally via intermediate storage in at least one storage vessel (if appropriate), wherein the synthesis, the hydrogenation in step iii) and any at least one storage vessel are fluidically connected to one another.

[0057] The nitric acid is generated in step i-1) c) from the ammonia and the oxygen-containing gas (eg air or oxygen) in a manner very familiar to the person skilled in the art, as described, for example, in document EP 0 808 797 A2, which is expressly incorporated herein in its entirety by reference.

[0058] The oxygen-containing gas used for the production of nitric acid in step i-1) c) is preferably oxygen. In step i-1) b) of the method according to the invention and in other embodiments, ammonia is provided to step i-1) c). For the supply of at least one organic nitro compound in step i-1), it is sufficient when the ammonia provided for the supply of nitric acid must be at least a direct process product of step i-1) b). This means that for the performance of the step of providing ammonia, it is sufficient to simply deliver the ammonia as a direct process product from at least step i-1) b) as a raw material from a storage container or a feed port. In this case, the manufacturer of the organic amine or organic nitro compound produced by the method according to the invention does not itself perform the above-mentioned step for the production of ammonia, but only ensures that the ammonia provided for the production of the organic amine or the production of the organic nitro compound is produced at least by using steps i-1) a) to c) and is therefore a direct process product thereof.

[0059] According to the invention, when providing ammonia, at least one of the above-mentioned reaction steps for producing ammonia is carried out as an integral step in the process for producing organic amines according to the invention, and the ammonia obtained in the process is sent to the synthesis of nitric acid after, optionally, intermediate storage in a storage container. Here, it is preferred that in step i-1) b), ammonia is provided as a direct process product of the ammonia production in the form of a material stream from the ammonia production via a fluid connection, via intermediate storage (if necessary) in at least one storage container, wherein the ammonia production, any necessary at least one storage container and the synthesis in step ii) are fluidically connected to each other.

[0060] In those embodiments of the invention in which nitric acid is provided directly as a material stream from a nitric acid production via a fluid connection between the synthesis in step i-2) and the hydrogenation in step iii) and, if appropriate, at least one storage container, it has also been found to be preferred that in step i-1) ammonia is provided as a direct process product of the ammonia production into a movable, closed transport container and optionally transferred from there to a storage container for intermediate storage, wherein the ammonia production and the nitric acid production are not fluidically connected to one another. In this case, the reverse is particularly preferred when the organic amine used for the synthesis of the organic isocyanate compound is produced by carrying out at least the following steps:

[0061] i) producing at least one organic nitro compound by a process for synthesizing at least one organic nitro compound, which comprises at least the following steps:

[0062] i-1) producing nitric acid by performing a nitric acid production process, the process comprising at least the following steps:

[0063] a) and b) providing ammonia as a direct process product of the reaction of at least nitrogen and hydrogen, the hydrogen being produced, in addition to oxygen, by using electricity produced from renewable energy sources in an electrolysis device and using water to perform an electrolysis of water;

[0064] c) producing nitric acid by reacting previously provided ammonia at least with an oxygen-containing gas in the production of nitric acid;

[0065] i-2) synthesizing at least one organic nitro compound, preferably at least one aromatic organic nitro compound, by nitrating at least one organic compound, preferably at least one aromatic organic compound, with at least said nitric acid;

[0066] ii) providing hydrogen, preferably by electrolysis of water in an electrolysis device,

[0067] where electricity generated from renewable energy sources is used;

[0068] iii) subjecting the at least one organic nitro compound and the provided hydrogen to a hydrogenation, and then hydrogenating the nitro group of the at least one organic nitro compound by its reduction by reaction with the hydrogen to obtain at least one organic amino compound, preferably at least one aromatic organic amino compound.

[0069] Ammonia is produced in step i-1) b) from nitrogen and the hydrogen provided in step i-1) a) in a manner very familiar to the person skilled in the art; for example, by the Haber-Bosch process, using known reactor technology and design of the process, which is expressly incorporated herein in its entirety by reference.

[0070] For the supply or production of nitric acid, it has been found to be preferred to provide the nitrogen for the production of ammonia in step i-1) b) by air fractionation. Air fractionation processes and corresponding ammonia production plants are part of the prior art and are available on the market.

[0071] The oxygen used in the oxidation reaction for producing nitric acid can likewise be provided by fractionation of air. Therefore, in another embodiment, a preferred method is characterized in that the nitric acid provided in step i-1) is a process product from nitric acid production, wherein at least one oxygen-containing gas (5e) selected from oxygen from the electrolysis of water, air or oxygen fractionated from air is used for the oxidation reaction in step c). When air fractionation is used to provide oxygen for the oxidation, it is particularly preferred when the nitric acid provided in step i-1) is a direct process product of nitric acid production, wherein in the oxidation reaction in step c), the oxygen-containing gas is provided as oxygen by air fractionation, and likewise nitrogen is provided for step i-1) b). In the production of ammonia for the production of nitric acid, in step i-1) a) of the present process, hydrogen must be provided by electrolysis of water, and the electrolysis of water is driven partly or completely by electricity provided by renewable energy sources as energy source.

[0072] Hydrogen can be provided in step ii) of the process for the hydrogenation in step iii) of the process, for example, by electrolysis of water or electrolysis of chlorine or a combination thereof, wherein the selected electrolysis is in each case driven partly or completely by electricity provided using renewable energy as energy source. In one embodiment of the process, it has been found to be advantageous when the hydrogen provided in step ii) is produced by electrolysis of water using electrical energy, wherein the supply of electrical energy as renewable energy source optionally uses wind energy, solar energy, hydroelectric power or a mixture thereof.

[0073] "Renewable energy" is understood by a person skilled in the art as energy from an inexhaustible energy source, such as wind energy, hydropower, bioenergy (e.g. conversion of biogas or biomass into electrical energy) or solar energy. Therefore, suitable renewable energy is most preferably one of wind energy, solar energy, hydropower or a mixture thereof. If renewable energy is used as an energy source within the scope of the present invention, in particular for the supply of electricity, it is possible to store the renewable energy when it is sufficient, advantageously ensuring the implementation of the process according to the invention in periods of shortage of renewable energy, for example, by storing it in the form of electrical energy in batteries to compensate for the shortage period.

[0074] The production of hydrogen by water electrolysis is an electrochemical conversion of water. Water is decomposed into hydrogen and oxygen using electrical energy here. A known process is proton exchange electrolysis (PEM electrolysis), which is described, for example, in EP 3489394 A. A further method is alkaline water electrolysis. The two methods are particularly different in process parameters, such as temperature, pressure and pH value. However, both methods produce target products, water and oxygen. The electrolysis of water can be carried out with prior art equipment. Industrial systems for the electrolysis of alkaline water and PEM electrolysis are well known and commercially available. The principle of the electrolysis of water is described by way of example in Chapter 6.3.4 of "Elektrochemische Verfahrenstechnik" [Electrochemical process technology] (2003 Wiley-VCH-Verlag; ISBN 3-527-29958-0) of Volkmar M.Schmidt.

[0075] In step iii) of the process of the present invention, at least one organic nitro compound from step i) and the hydrogen provided in step ii) of the process are introduced into a hydrogenation. The nitro group of the at least one organic nitro compound is then reduced by reaction with the hydrogen to achieve hydrogenation.

[0076] The performance of hydrogenating organic nitro compounds with hydrogen is very well known to the person skilled in the art. Correspondingly available hydrogenation reactions which can be used in step iii) are known to the person skilled in the art; for example, from the following journals: Gerald Booth (2007), Ullmanns der Industriechemie, Weinheim, Wiley VCH, doi: 10.1002 / 14356007.a17_411, which is expressly incorporated herein in its entirety by reference.

[0077] Another embodiment of the preferred process according to the invention is characterized in that the organic amino compound obtained in step iii) is selected from toluenediamine (TDA), methylenedianiline (MDA), preferably in turn selected from diphenylmethane-2,2'-diamine, diphenylmethane-2,4'-diamine, diphenylmethane-4,4'-diamine or mixtures thereof, or mixtures thereof.

[0078] The organic amino compound produced by the method of the present invention is preferably suitable for the synthesis of organic isocyanates. In another preferred embodiment of the method of the present invention, at least the following steps are performed to synthesize organic isocyanates:

[0079] iv) synthesis of phosgene from at least carbon monoxide and chlorine;

[0080] v) Isocyanate production of organic isocyanates by reaction of at least one phosgene with at least one organic amino compound with release of hydrogen chloride.

[0081] Therefore, the present invention further provides a method for synthesizing organic isocyanate, which at least comprises the following steps:

[0082] providing at least one organic amino compound as a direct process product of the above-described method for producing an organic amine for synthesizing an organic isocyanate compound;

[0083] Synthesis of phosgene from at least carbon monoxide and chlorine;

[0084] Isocyanate production of organic isocyanates by reaction of at least one phosgene with at least one organic amino compound with release of hydrogen chloride.

[0085] When at least one organic amino compound is provided, the direct process product of the above-described method for producing an organic amine is provided for the synthesis of an organic isocyanate compound. All preferred embodiments of the process for producing an organic amine for the synthesis of an organic isocyanate compound are also to be considered preferred in the process step.

[0086] Phosgene can be synthesized industrially, for example, by converting chlorine and carbon monoxide at high temperatures over specific activated carbon catalysts, consuming energy, for example, for cooling the reaction zone and increasing the temperature. For this purpose, the conventional method on an industrial scale is to use a tubular furnace equipped with activated carbon. The corresponding apparatus and methods for the synthesis of phosgene are very familiar to the person skilled in the art.

[0087] In order to provide gaseous chlorine for phosgene synthesis, the person skilled in the art will be very familiar with the following methods for producing chlorine by electrochemical oxidation: electrolysis of hydrochloric acid using gas diffusion electrodes (also known as HCl ODC electrolysis process (ODC=oxygen-consuming electrode); suitable electrolysis cells are described in US, 6022,634A, WO 03 / 31690A1), chlorine production by diaphragm electrolysis of hydrochloric acid (see EP 1 103636 A1), production of chlorine by thermal catalytic gas phase oxidation (see WO 2012 / 025483 A2), production of chlorine by chlor-alkali electrolysis (see WO 2009 / 007366 A2). The contents of the above-mentioned documents relating to chlorine production are expressly incorporated herein in their entirety by reference. Therefore, the following embodiments of the method of the present invention are preferred, in which chlorine is provided by at least one chlorine synthesis, which is selected from the following chlorine synthesis

[0088] A) oxidative conversion of hydrogen chloride, which is separated from the isocyanate production and purified with oxygen in a thermal catalytic gas phase oxidation to produce chlorine and water,

[0089] B) Reaction of purified hydrogen chloride from isocyanate production with water to form hydrochloric acid, optionally purified, and electrochemical oxidation of the hydrochloric acid to chlorine in the presence or absence of hydrogen.

[0090] In a preferred variant of the embodiment of the process, the chlorine required for the synthesis of phosgene is produced electrolytically, in particular by electrochemical oxidation in hydrochloric acid electrolysis using gas diffusion electrodes, by electrochemical oxidation in hydrochloric acid diaphragm electrolysis, or by electrochemical oxidation in chloralkali electrolysis. It is in turn particularly preferred here when the electricity used in the electrochemical oxidation in each case comes from renewable energy sources, in particular from renewable energy sources in the form of wind energy, solar energy or hydropower.

[0091] In another preferred embodiment of the process, the carbon monoxide required for the synthesis of phosgene is produced from CO2 by at least one method selected from the following

[0092] A) electrochemical reduction of carbon dioxide using electricity generated from renewable energy,

[0093] B) a reforming process for converting methane, preferably biomethane, and steam into carbon monoxide at a temperature of at least 500° C. with the addition of at least CO 2 ,

[0094] C) Hydrogen and carbon dioxide are converted to carbon monoxide in a reverse water gas shift (RWGS) reaction zone.

[0095] For example, those skilled in the art know from the document WO 2021 / 069470 A that electrodes and methods for performing electrochemical reduction of CO2 are used. More preferably, electrochemical reduction of CO2 is performed by the method of WO 2021 / 069470 A. The document is expressly and fully incorporated herein by reference. In this preferred electrolytic method for producing carbon monoxide, carbon monoxide, optional hydrogen and chlorine are obtained by electrochemical conversion of carbon dioxide and alkali chloride solution. This preferred electrolytic method is characterized in that carbon dioxide is used as a cathode at a gas diffusion electrode and electrochemically reduced in an aqueous solution containing alkali chloride as a cathode electrolyte, while chlorine is produced anode-wise in an aqueous solution containing alkali chloride as an anolyte, wherein an alkali metal salt of carbonic acid (selected from alkali carbonate, alkali bicarbonate or a mixture thereof) formed in the cathode electrolyte subsequently reacts with hydrogen chloride to generate carbon dioxide and alkali chloride, and the released carbon dioxide is returned to the cathode space of the gas diffusion electrode, and the produced alkali chloride is returned to the anode space and / or cathode space.

[0096] A suitable reforming process is described in PCT application number PCT / EP2022 / 052267, in which methane (preferably biomethane) and steam are converted into carbon monoxide at a temperature of at least 500°C by adding at least CO2 and supplementary heat energy, which is expressly incorporated herein in its entirety by reference. The present method involves the preparation of carbon dioxide from methane, steam and CO2, which is used to prepare phosgene for the synthesis of organic isocyanates, and comprises at least the following steps:

[0097] Synthesis of carbon monoxide in a reforming process, wherein methane and steam are converted into a product gas containing carbon monoxide at a temperature of at least 500° C., with the addition of at least carbon dioxide and supplementary heat;

[0098] washing the carbon monoxide-containing product gas obtained from the above synthesis, at least by removing CO2, and optionally additionally by at least one removal selected from the group consisting of removing water, removing hydrogen or a combination thereof, to obtain carbon monoxide;

[0099] The added CO2 is provided to the reforming process, which is provided at least by the removal of CO2 from the washing step described above.

[0100] The condition is

[0101] 1) The heat energy provided to the reforming process for carbon monoxide synthesis is provided by at least one method selected from: (i) burning a hydrogen-containing fuel produced using renewable energy, (ii) burning a methane-containing fuel from a biogenic source, (iii) converting electrical energy produced from renewable energy into heat; or

[0102] 2) additionally providing CO2 from another CO2 source for providing CO2 added to the synthesis in the above-mentioned reforming process; or

[0103] 3) A combination of options 1) and 2) above.

[0104] A useful methane source for the reforming process is more preferably methane from biological sources. Those skilled in the art understand that "methane from biological sources" (also known as "biomethane") refers to methane obtained industrially from biomass by methane fermentation, rather than fossil methane. As is well known, methane fermentation refers to the anaerobic degradation of organic matter by microorganisms. For example, in a biogas plant, both organic waste and renewable raw materials are fermented accordingly to produce methane from biological sources.

[0105] In a particularly preferred embodiment of the phosgene production process for isocyanate synthesis according to the present invention, carbon monoxide prepared from CO2 is used for phosgene synthesis, in particular for phosgene synthesis in step iv, by at least one reaction of hydrogen and CO2 in a reverse water gas shift (RWGS) reaction zone to form carbon monoxide. For example, such an embodiment is described in document WO 2021 / 089737 A, which is expressly incorporated herein in its entirety by reference.

[0106] A "reaction zone" is a portion of the reaction space where a chemical reaction (e.g., a reverse water gas shift reaction) takes place. A "reaction chamber" is a volume where co-reactants that participate in a chemical reaction are brought together and the chemical reaction takes place. For a chemical reaction, this can, for example, be the volume of a container where reactants (e.g., carbon dioxide in an RWGS reaction) and co-reactants (hydrogen in an RWGS reaction) are present together and react in the reaction zone.

[0107] In this particularly preferred method, for the production of carbon monoxide, at least the following steps are particularly preferably carried out:

[0108] the carbon dioxide gas stream is purified, optionally by adsorption, gas scrubbing or catalytic treatment to remove its secondary components, in particular nitrogen oxides, sulfur compounds, dust, water, oxygen and HCl, to obtain purified carbon dioxide,

[0109] The provided hydrogen gas is fed into the RWGS reaction zone together with the purified carbon dioxide gas stream, and the reactants are reacted according to the RWGS reaction principle to generate a product gas mixture consisting of steam, CO and possible by-products, especially low-order hydrocarbons, and methane is particularly preferred.

[0110] unreacted carbon dioxide is separated from the gas mixture of the RWGS reaction, in particular by amine scrubbing, and the unreacted carbon dioxide is recycled into the RWGS reaction, hydrogen which has not reacted in the RWGS reaction is separated from the gas mixture of carbon monoxide and hydrogen obtained after the separation, in particular using a cold box, and optionally the hydrogen is recycled into the RWGS reaction or the hydrogen is fed into the hydrogenation of the organic nitro compound,

[0111] The carbon monoxide remaining after separation is introduced into the phosgene synthesis.

[0112] As mentioned above, the organic amino compound produced by the method of the present invention is preferably suitable for the synthesis of organic isocyanates. In another preferred embodiment of the method of the present invention, at least the following steps are additionally performed to synthesize organic isocyanates:

[0113] iv) synthesizing phosgene from at least carbon monoxide and chlorine (8b);

[0114] v) Isocyanate production of organic isocyanates by reaction of at least one phosgene with at least one organic amino compound with release of hydrogen chloride.

[0115] Wherein, for the production of carbon monoxide, at least the following steps are performed:

[0116] the carbon dioxide gas stream is purified, optionally by adsorption, gas scrubbing or catalytic treatment, to remove its secondary components, in particular nitrogen oxides, sulfur compounds, dust, water, oxygen and HCl, to obtain purified carbon dioxide,

[0117] The hydrogen provided in step ii) is fed into the RWGS reaction zone together with the purified carbon dioxide gas stream, and the reactants are reacted according to the RWGS reaction principle to generate a product gas mixture consisting of steam, CO and possible by-products, especially lower hydrocarbons, and methane is particularly preferred.

[0118] separating unreacted carbon dioxide from the gas mixture of the RWGS reaction, in particular by amine scrubbing, and recycling the unreacted carbon dioxide into the RWGS reaction, separating hydrogen which has not reacted in the RWGS reaction from the gas mixture of carbon monoxide and hydrogen obtained after the separation, in particular using a cold box, and optionally recycling the hydrogen into the RWGS reaction or feeding the hydrogen into the hydrogenation of the organic nitro compound,

[0119] The carbon monoxide remaining after separation is introduced into the phosgene synthesis.

[0120] The CO2 source for providing carbon monoxide for the above steps A) and / or B) and / or C) is, for example, CO2 emitted when providing heat energy for step B) or C), CO2 emitted when air is fractionated to provide nitrogen for ammonia, or CO2 from an external CO2 source.

[0121] As a kind of external CO2 source, the CO2 of its contribution is not discharged by the method of the present invention or its embodiment.External CO2 source can be, for example, the CO2 formed in the waste gas produced during cement production or fuel combustion (such as waste incineration), or the CO2 obtained from air.In a preferred embodiment of the inventive method, from external CO2 source can be selected from process gas or waste gas of at least one process such as (i) from cement production, H2 production, incineration by absorbing, and / or (ii) from air by introducing CO2 component in alkali metal hydroxide solution (such as potassium hydroxide solution).This causes the formation of potassium bicarbonate, and potassium bicarbonate can be thermally decomposed back to carbon dioxide and potassium hydroxide then.Then the released carbon dioxide is sent into the process of the present invention for synthesizing carbon monoxide.

[0122] The RWGS reaction is preferably carried out in the presence of at least one catalyst. The latter is more preferably selected from at least one compound in the following group:

[0123] (I)Formula A (1-w-x) A' w A" x B (1-y-z) B' y B" z O 3-δ Mixed metal oxides

[0124] in

[0125] A, A' and A" are each independently selected from: Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, Sn, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Tl, Lu, Ni, Co, Pb, Bi and / or Cd; and

[0126] B, B' and B" are each independently selected from: Cr, Mn, Fe, Bi, Cd, Co, Cu, Ni, Sn, Al, Ga, Sc, Ti, V, Nb, Ta, Mo, Pb, Hf, Zr, Tb, W, Gd, Yb, Mg, Li, Na, K, Ce and / or Zn; and

[0127] 0≤w≤0.5; 0≤x<0.5; 0≤y≤0.5; 0≤z≤0.5 and -1≤δ≤1;

[0128] (II)Formula A(1-w-x) A' w A" x B (1-y-z) B' y B" z O 3-δ A mixed metal oxide, wherein

[0129] A, A' and A" are each independently selected from: Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Tl, Lu, Ni, Co, Pb and / or Cd; and

[0130] B is selected from the group consisting of: Cr, Mn, Fe, Bi, Cd, Co, Cu, Ni, Sn, Al, Ga, Sc, Ti, V, Nb, Ta, Mo, Pb, Hf, Zr, Tb, W, Gd, Yb, Mg, Cd, Zn, Re, Ru, Rh, Pd, Os, Ir and / or Pt; and

[0131] B' is selected from: Re, Ru, Rh, Pd, Os, Ir and / or Pt; and B" is selected from: Cr, Mn, Fe, Bi, Cd, Co, Cu, Ni, Sn, Al, Ga, Sc, Ti, V, Nb, Ta, Mo, Pb, Hf, Zr, Tb, W, Gd, Yb, Mg, Cd and / or Zn;

[0132] and

[0133] 0≤w≤0.5; 0≤x≤0.5; 0≤y≤0.5; 0≤z≤0.5 and -1≤δ≤1;

[0134] (III) a mixture of at least two different metals M1 and M2, the support of which comprises an oxide of Al, Ce and / or Zr doped with the metal M3;

[0135] Wherein: M1 and M2 are each independently selected from: Re, Ru, Rh, Ir, Os, Pd and

[0136] and / or Pt; and

[0137] M3 is selected from: Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and / or Lu;

[0138] (IV) LO x (M (y / z) Al (2-y / z) O3) z A mixed metal oxide; wherein

[0139] L is selected from: Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, Sn, Pb, Pd, Mn, In, Tl, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and / or Lu; and

[0140] M is selected from: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Zn, Cu, Ag and / or Au;

[0141] and

[0142] 1 < x ≤ 2; 0 < y ≤ 12 and 4 ≤ z ≤ 9;

[0143] (V) Mixed metal oxide of LO(Al2O3) z wherein

[0144] L is selected from: Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, Sn, Pb, Mn, In, Tl, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and / or Lu; and

[0145] 4 ≤ z ≤ 9;

[0146] (VI) Oxidation catalyst containing Ni and Ru;

[0147] (VII) Metal M1 and / or at least two different metals M1 and M2 on a support and / or

[0148] or in a support, wherein the support

[0149] is a carbide, oxycarbide, carbonitride, nitride, boride, silicide, germanide and / or selenide of metals A and B; wherein:

[0150] M1 and M2 are each independently selected from: Cr, Mn, Fe, Co, Ni, Re, Ru, Rh, Ir, Os, Pd, Pt, Zn, Cu, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and / or Lu; and

[0151] A and B are each independently selected from: Be, Mg, Ca, Sc, Ii, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Hf, Ta, W, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and / or Lu;

[0152] and / or

[0153] The reaction products of (I), (II), (III), (IV), (V), (VI) and / or (VII) in the presence of carbon dioxide, hydrogen, carbon monoxide and / or water at a temperature ≥ 700°C.

[0154] In a particularly preferred embodiment of the process according to the invention, which has phosgene production for isocyanate synthesis and pyrolysis of organic material for producing the organic compound used in step i-2), the carbon monoxide is provided by converting the residue from the gasification into carbon dioxide in a combustion and introducing the optionally purified carbon dioxide into the process for providing carbon monoxide.

[0155] Therefore, particularly preferred is an embodiment of the method according to the invention which additionally comprises

[0156] The at least one organic compound used in step i-2) is an aromatic organic compound which is provided as a direct process product from a process comprising at least the following steps:

[0157] Pyrolyzing the organic material at a temperature of 600 to 1000°C to obtain a gaseous pyrolysis product and a pyrolysis residue;

[0158] contacting the gaseous pyrolysis product with a heterogeneous catalyst to obtain a conversion product containing at least one aromatic organic compound having a molecular weight of less than 300 g / mol,

[0159] processing the conversion product to obtain said aromatic organic compound, in particular an aromatic organic compound selected from benzene, toluene or xylene,

[0160] The following steps are additionally performed:

[0161] Gasifying the pyrolysis residue after pyrolysis of organic materials to provide at least carbon monoxide, which is fed to phosgene synthesis;

[0162] The residual material from the combustion gasification is converted to provide carbon dioxide and the optionally purified carbon dioxide is introduced into a process for providing carbon monoxide for phosgene synthesis, which is selected from

[0163] A) electrochemical reduction of carbon dioxide using electricity generated from renewable energy,

[0164] B) a reforming process of converting methane and steam into carbon monoxide at a temperature of at least 500° C. with the addition of at least CO 2 and supplemental thermal energy;

[0165] C) Hydrogen and carbon dioxide are converted to carbon monoxide in a reverse water gas shift (RWGS) reaction zone.

[0166] The invention also provides a device which is arranged for the production of organic amino compounds for the production of organic isocyanate compounds. In this device arrangement, the device part for providing nitric acid is filled with nitric acid, which is a direct process product of the nitric acid production process, which comprises at least the following steps:

[0167] a) Providing hydrogen and oxygen by electrolysis of water using water in an electrolysis device, wherein the electricity used comes from renewable energy sources;

[0168] b) in ammonia synthesis, producing ammonia by reacting at least nitrogen and hydrogen from the electrolysis of said water;

[0169] c) producing nitric acid by reacting previously produced ammonia in the production of nitric acid at least with an oxygen-containing gas, preferably at least one oxygen-containing gas selected from oxygen produced by electrolysis of said water, air or oxygen from air fractionation.

[0170] In particular, the device according to the present invention is a device configured for producing an organic amino compound, wherein the device comprises at least one hydrogen supply device, at least one device for producing an organic nitro compound, at least one organic nitro compound hydrogenation device and at least one nitric acid supply device, wherein

[0171] - at least one nitric acid supply device, comprising at least one nitric acid outlet and at least one nitric acid inlet and at least one nitric acid space;

[0172] - at least one device for producing an organic nitro compound, comprising at least one reactor, at least one inlet for an organic compound, at least one inlet for nitric acid and at least one outlet for an organic nitro compound;

[0173] - at least one hydrogenation unit for an organic nitro compound, comprising at least one reactor, at least one inlet for an organic nitro compound, at least one inlet for hydrogen and at least one outlet for an organic amino compound;

[0174] It is characterized by that in terms of setting

[0175] i) The nitric acid space is filled with nitric acid, which is a direct process product of a nitric acid production process, which process comprises at least the following steps:

[0176] a) Providing hydrogen and oxygen by electrolysis of water using water in an electrolysis device, wherein the electricity used comes from renewable energy sources;

[0177] b) in ammonia synthesis, the production of ammonia by reaction of at least nitrogen and hydrogen from the electrolysis of water as described above

[0178] c) producing nitric acid by reacting previously produced ammonia in the production of nitric acid at least with an oxygen-containing gas, preferably at least one oxygen-containing gas selected from oxygen produced by electrolysis of said water, air or oxygen from air fractionation.

[0179] ii) a nitric acid outlet of the device for supplying nitric acid is fluidly connected to a nitric acid inlet of the device for producing organic nitro compounds;

[0180] iii) the organic nitro compound outlet of the organic nitro compound production device is fluidly connected to the organic nitro compound inlet of the organic nitro compound hydrogenation device;

[0181] iv) The hydrogen inlet of the device for hydrogenating the organic nitro compound is fluidly connected to the hydrogen outlet of the device for supplying hydrogen.

[0182] In the device for providing nitric acid, the space for nitric acid can, for example, be the space of a storage container or the space of a pipeline. If the space is a storage container, then in another embodiment, when the device additionally comprises at least one discharge device for transporting the container, the discharge device is preferably connected to the inlet fluid of the device for providing nitric acid.

[0183] However, in a particularly preferred embodiment of the device according to the invention, the device is characterized in that the space for the nitric acid is the space of a pipeline and the nitric acid inlet of the device for providing nitric acid is fluidically connected to the outlet of the device for producing nitric acid.

[0184] Furthermore, it has been found that, in the context of the process according to the invention, it is preferred to use at least one electrolysis device to provide hydrogen for the hydrogenation of the organic nitro compound, which electrolysis device is selected from at least one of a water electrolysis device, an alkali metal chloride electrolysis device and a hydrochloric acid electrolysis device. For example, a water electrolysis device for providing hydrogen for the production of nitric acid can also be used accordingly to provide hydrogen for the hydrogenation device and can be integrated into the overall device accordingly.

[0185] The device according to the invention for providing an organic amino compound is preferably a component of a device for providing an organic isocyanate compound and is characterized in that, in this embodiment, the outlet for the organic amino compound of the device for hydrogenating the organic nitro compound is fluidically connected to the inlet for the organic amino compound of the phosgenation device, wherein the device for phosgenation comprises at least one inlet for phosgene, at least one inlet for the organic amino compound and at least one outlet for the organic isocyanate compound.

[0186] The present invention also provides nitric acid, which is a direct process product of a production process, comprising at least the following steps:

[0187] a) Providing hydrogen and oxygen by electrolysis of water using water in an electrolysis device, wherein the electricity used comes from renewable energy sources;

[0188] b) in the ammonia synthesis, providing ammonia by reacting at least nitrogen and hydrogen from the electrolysis (5) of said water;

[0189] c) producing nitric acid by reacting previously produced ammonia in the production of nitric acid at least with an oxygen-containing gas, preferably at least one oxygen-containing gas selected from oxygen produced by electrolysis of said water, air or oxygen from air fractionation.

[0190] Use for producing organic amino compounds for synthesizing organic isocyanate compounds.

[0191] The following examples refer to Figures 1 to 6 The present invention is described in detail. Figure 7 The method according to the prior art is shown. The reference numbers on the right side of the figure are defined as follows:

[0192] 1 Phosgene synthesis

[0193] 1a Phosgene

[0194] 2 Isocyanate production

[0195] 3 Hydrogen supply (particularly as hydrogen 5a from the electrolysis 5 of water or from the electrolysis 3b of water)

[0196] 3a Hydrogen from a hydrogen supply

[0197] 3b Electrolysis of water

[0198] 3c O2 from the electrolysis of water in the hydrogen supply 3b

[0199] 4CO2 gas, purified

[0200] 5. Electrolysis of water

[0201] 5a Hydrogen supply from water electrolysis 5

[0202] 5b Oxygen from the electrolysis of water

[0203] 5c for water electrolysis 5 water

[0204] 5d Hydrogen from the electrolysis of water

[0205] 5e Oxygen-containing gas for HNO3 synthesis (preferably from water electrolysis and / or air fractionation and / or air)

[0206] 5f Oxygen from air fractionation (O2)

[0207] 6 Reforming process for producing CO from hydrogen 3a and carbon dioxide (not shown, optionally additionally from 27) using RWGS (reverse water gas shift)

[0208] 6a Reforming process to produce H2 from methane and water using water gas shift

[0209] 6b Reforming process of producing carbon monoxide from methane and water in a steam-methane reforming reactor

[0210] 7 Carbon monoxide CO

[0211] 8Chlorine Synthesis

[0212] 8a H2 from chlorine synthesis

[0213] 8b Cl2 from chlorine synthesis

[0214] 9 Renewable energy for water electrolysis 3b

[0215] 10 Renewable energy for water electrolysis 5

[0216] 11Renewable energy for chlorine electrolysis 8

[0217] 12 Renewable energy for air fractionation 23

[0218] 13 Residue from pyrolysis 25

[0219] 14CO from gasification 26

[0220] 15 Residue from gasification 26

[0221] 16 Organic scrap materials, preferably scrap materials containing polyurethane

[0222] 17 Organic amines, such as diaminotoluene

[0223] 18Organic isocyanates, such as toluene diisocyanate (TDI)

[0224] 19 Preparation of organic nitro compounds

[0225] 19a Organic nitro compounds such as dinitrotoluene

[0226] 19b Organic compounds requiring nitration from pyrolysis of 25

[0227] 19c Organic compounds that need to be nitrated, such as toluene

[0228] 20 Hydrogenation of nitro compounds

[0229] 21 Ammonia synthesis

[0230] 21a Nitrogen for the synthesis of ammonia

[0231] 21b Ammonia Supply

[0232] 22 Nitric Acid Production

[0233] 22a Supply of nitric acid

[0234] 23 N2 supply through air fractionation

[0235] 24 Air used to produce HNO3

[0236] 25 Pyrolysis of organic materials, especially polyurethane materials

[0237] 26 Gasification of organic materials, such as residues from pyrolysis 25

[0238] 26a H2 from gasification 26

[0239] 27 Burning

[0240] 27a Purified CO2 gas from combustion 27

[0241] 28Process Gas Treatment

[0242] The arrows in the figures indicate the flow of material, energy or heat between the process steps / plant components carried out by the corresponding process steps. The process features indicated by dashed lines indicate additional features of other preferred embodiments. The dashed arrows indicate the supply of a certain material, which can be transported from one process step to the next process step by means of a closed transport container or by means of a material flow connected by a fluid. The arrow connecting two process steps with a solid line indicates the material flow of the material shown, which is transported in the direction of the arrow by means of a fluid connection between the process steps connected by the arrow.

[0243] Figure 1A method for producing an organic amino compound by hydrogenation of an organic nitro compound 20 is illustrated, wherein firstly, an organic nitro compound 19a and hydrogen 3a from a hydrogen supply 3 are converted into an organic amino compound 17, wherein the produced organic nitro compound 19a is produced in the production of organic nitro compounds 19, wherein an organic compound 19c is reacted with nitric acid, and the nitric acid 22a provided for this purpose is a direct process product of the nitric acid production 22, wherein ammonia 21b is provided by hydrogen, which is produced from the electrolysis 5 of water, using water 5c and renewable energy sources, and the nitric acid is formed by the reaction of nitrogen 21a, preferably from air fractionation 23, with oxygen 5e, such as air 24 or oxygen 5b from the electrolysis 5 of water or oxygen 5f from air fractionation 23. The ammonia 21b provided and the nitric acid 22a provided are produced by corresponding methods, preferably at the same location as the organic amino compound, and are both provided as material streams via a fluid connection to the respective further conversion. In this case, excess hydrogen 5a from the electrolysis 5 of water can be used for the hydrogen supply 3 in order to introduce hydrogen 3a into the hydrogenation 20 of the nitro compound and to introduce it via a fluid connection.

[0244] according to Figure 1 An equally possible variant is to produce nitric acid in a decentralized manner by the above process so that it can be transported in transport containers according to the supply of nitric acid for the production of organic nitro compounds 19. This variant is Figure 2 As shown, ammonia is provided for the supply of ammonia 21b and introduced into the production of nitric acid 22 via a fluid connection.

[0245] However, according to Figure 1 And if Figure 3 As shown, it is equally possible to produce ammonia in a decentralized manner, for example by the aforementioned method, so that it is transported in a transport container to supply ammonia 21b, the purpose of which is to convert the ammonia into nitric acid in the supply of nitric acid 22, which is then provided via a fluid connection and introduced into the production of organic nitro compounds 19.

[0246] Figure 1 The method for supplying an organic amino compound shown in can be incorporated into these conversions of organic amino compounds into organic isocyanate compounds. In this case, an organic amino compound 17 obtained by hydrogenation 20 of an organic nitro compound is introduced into phosgenation 2 and reacted with phosgene 1a to give an organic isocyanate compound 18. The phosgene 1a used for this purpose is produced in phosgene production 1 from chlorine 8b and carbon monoxide 7, wherein the carbon monoxide 7 is produced by reforming 6 of RWGS from hydrogen 3a and carbon dioxide (feed not shown). The hydrogen 3a comes from the supply of hydrogen 3, in Figure 2 and Figure 3In case of decentralized supply of ammonia or nitric acid, preferably water from electrolysis of water 3b is produced by water and renewable energy sources 9. In case of supply of ammonia and nitric acid by fluid connection, preferably hydrogen 3a is provided by using electrolysis 5 of water.

[0247] according to Figures 1 to 3 , chlorine 8b is provided by chlor-alkali electrolysis 8, using electricity from renewable energy sources 11, wherein any hydrogen 8a formed is removed to provide hydrogen 3 and used in the hydrogenation 20 of organic nitro compounds.

[0248] exist Figures 1 to 3 In the process, the carbon monoxide 14 produced in addition preferably comes from the gasification 26 of organic substances, more preferably from the residue 13 of the pyrolysis 25 of organic materials. The oxygen 3c produced by the electrolysis (3b) of water is preferably used for the gasification 26. The residue 15 from the gasification 26 is in turn preferably converted into carbon dioxide in combustion using the oxygen 3c from the electrolysis (3b) of water. The obtained carbon dioxide is purified and fed as purified carbon dioxide 27a to the reforming process 6 with RWGS. The hydrogen 26a produced by the gasification 26 is provided to the hydrogen supply 3.

[0249] according to Figures 1 to 3 The organic compound 19c used for nitrifying the organic compound 19 may at least partly come from the pyrolysis 25 of organic waste 16, preferably plastic waste, in particular polyurethane material waste.

[0250] Figure 4 The entire process flow of Inventive Example 1 is shown (see therein).

[0251] Figure 5 and Figure 6 Shows Figure 4 A variation of Example 1, wherein Figure 2 or Figure 3 By analogy, ammonia or nitric acid is only available in a decentralized manner through the above process.

[0252] Figure 7 Embodiment 2 based on the prior art is shown.

[0253] Further embodiments of the invention are considered to be the following aspects I to XXVI.

[0254] I. A method for producing an organic amino compound for synthesizing an organic isocyanate compound, comprising at least the following steps: i) providing at least one organic nitro compound (19a) as a process product of a process (19) for synthesizing at least one organic nitro compound (19a), comprising at least the following steps:

[0255] i-1) providing nitric acid (22a) as a process product of a nitric acid production process, which comprises at least the following steps:

[0256] a) Providing hydrogen (5d) and oxygen (5b) by electrolysis (5) of water in an electrolysis device using electricity (10) from renewable energy sources and using water

[0257] (5c);

[0258] b) providing ammonia (21b) as at least nitrogen (21a) in ammonia synthesis (21)

[0259] a process product of the reaction with hydrogen (5d) from the electrolysis (5) of said water;

[0260] c) producing nitric acid (22b) by reacting previously provided ammonia (21b) at least with an oxygen-containing gas (5e) in a nitric acid production (22);

[0261] i-2) synthesizing (19) at least one organic nitro compound (19a), preferably at least one aromatic organic nitro compound (19a), by nitrating at least one organic compound (19b, 19c), preferably at least one aromatic organic compound (19b, 19c), using at least the nitric acid (22a) provided;

[0262] ii) providing (3) hydrogen (3a), preferably by electrolysis of water in an electrolysis device (3b) using electricity generated from a renewable energy source (9);

[0263] iii) introducing the provided at least one organic nitro compound (19a) and the provided hydrogen into a hydrogenation (20), and then hydrogenating (20) the nitro group of the at least one organic nitro compound by reduction thereof by reaction with the hydrogen (3a) to obtain at least one organic amino compound (17), preferably at least one aromatic organic amino compound (17).

[0264] II. A method according to aspect I, characterized in that the organic nitro compound (19a) is provided as a process product of the synthesis (19) in step i-2) in the form of a material flow directly from the synthesis (19) via a fluid connection, via intermediate storage (if necessary) in at least one storage container, wherein the synthesis (19), any necessary at least one storage container and the hydrogenation in step iii) are fluidically connected to each other.

[0265] III. A method according to aspect I, characterized in that the organic nitro compound (19a) from step i-2) is provided as a process product of the synthesis (19) into a movable closed transport container and is optionally transferred therefrom into a storage container for intermediate storage,

[0266] The synthesis (19) and the hydrogenation (20) in step iii) are not fluidically connected to one another.

[0267] IV. A method according to any one of aspects I to III, characterized in that in step i-1), nitric acid (22b) as a process product of the nitric acid production (22) is provided in the form of a material flow directly from the nitric acid production (22) via a fluid connection, via intermediate storage (if necessary) in at least one storage container, wherein the nitric acid production (22), any necessary at least one storage container and the synthesis (19) in step i-2) are fluidically connected to each other.

[0268] V. A method according to aspect IV, characterized in that, in step i-1), ammonia (21b) as a process product of the ammonia production (21) is provided in a movable closed transport container and optionally transferred therefrom to a storage container for intermediate storage,

[0269] The ammonia production (21) and the nitric acid production (22) are not fluidically connected to each other.

[0270] VI. A method according to aspects I to III, characterized in that in step i-1), nitric acid (22b) is provided as a process product of nitric acid production (22) into a movable closed transport container and optionally transferred from it into a storage container for intermediate storage,

[0271] Wherein the nitric acid production (22) and the synthesis (19) in step ii) are not fluidically connected.

[0272] VII. A method according to aspects I to VI, characterized in that the nitric acid (22a) provided in step i-1) is a process product from nitric acid production (22), wherein the nitrogen (21a) used to produce ammonia (21b) in step b) is provided by air fractionation (23).

[0273] VIII. A method according to aspects I to VII, characterized in that the nitric acid (22a) provided in step i-1) is a process product from nitric acid production (22), wherein at least one oxygen-containing gas (5e) selected from oxygen (5b) from electrolysis of water (5, 3b), air (24) or oxygen (5f) from air fractionation (23) is used for the oxidation reaction in step c).

[0274] IX. A method according to any one of aspects VII or VIII, characterized in that the nitric acid (22a) provided in step i-1) is a process product from nitric acid production (22), wherein the oxygen of the oxygen-containing gas (5f) used for the oxidation reaction in step c is provided by air fractionation (23), in particular the air fractionation (23) that also provides nitrogen (21a) for step b) in aspect 5.

[0275] X. A method according to any one of aspects I to IX, characterized in that the hydrogen provided in step ii) is produced at least by electrolysis (3b) of water using electrical energy (9), wherein the supply of electrical energy (9) is a renewable energy source, optionally using wind energy, solar energy, hydropower or a mixture thereof.

[0276] XI. The method according to any one of the above aspects, characterized in that the organic compound (19b, 19c) used in step i-2) is selected from benzene or toluene.

[0277] XII. A method according to any one of the above aspects, characterized in that at least one organic compound (19c) used in step i-2) is an aromatic organic compound (19b) provided as a direct process product from a process comprising at least the following steps:

[0278] Pyrolyzing (25) an organic material at a temperature of 600 to 1000° C. to obtain a gaseous pyrolysis product and a pyrolysis residue (13);

[0279] contacting the gaseous pyrolysis product with a heterogeneous catalyst to obtain a conversion product containing at least one aromatic organic compound having a molecular weight of less than 300 g / mol;

[0280] The conversion product is processed to obtain said aromatic organic compound, in particular an aromatic organic compound selected from benzene, toluene or xylene.

[0281] XIII. A method according to aspect XII, characterized in that the pyrolysis residue (13) obtained by pyrolysis (25) is converted into carbon monoxide (14), hydrogen (26a) and residue material (15) through partial oxidation gasification (26), and the carbon monoxide (14) formed after optional processing enters the phosgene synthesis (1), and the hydrogen (26a) is introduced into the hydrogen supply (3) of step ii) of this method.

[0282] XIV. The method according to any of the above aspects is characterized in that the organic amino compound (17) obtained in step iii) is selected from toluenediamine (TDA), methylenedianiline (MDA), (preferably selected in sequence from diphenylmethane-2,2'-diamine, diphenylmethane-2,4'-diamine, diphenylmethane-4,4'-diamine or a mixture thereof) or a mixture thereof.

[0283] XV. A method according to any one of the above aspects, characterized in that, for the synthesis of organic isocyanate, at least the following steps are additionally performed:

[0284] iv) synthesizing (1) phosgene (1a) from at least carbon monoxide (7) and chlorine (8b);

[0285] v) Production of isocyanates (2) from organic isocyanates (18) by reaction of at least one phosgene (1a) with at least one organic amino compound (17) with release of hydrogen chloride.

[0286] XVI. A method for synthesizing an organic isocyanate (18), comprising the following steps

[0287] providing at least one organic amino compound (17) as a process product of the method according to any one of aspects I to XIV;

[0288] Synthesis (1) of phosgene (1a) from at least carbon monoxide (7) and chlorine (8b);

[0289] Production of an isocyanate (2) of an organic isocyanate (18) by at least phosgene (1a)

[0290] It reacts with at least one organic amino compound (17) to generate and release hydrogen chloride.

[0291] XVII. A method according to any one of aspects XV or XVI, characterized in that carbon monoxide (7) is produced from CO2 by at least one method (6) selected from the following

[0292] A) electrochemical reduction of carbon dioxide using electricity generated from renewable energy,

[0293] B) a reforming process for converting biomethane and steam into carbon monoxide at a temperature of at least 500° C. with the addition of at least CO 2 ,

[0294] C) Hydrogen and carbon dioxide are converted to carbon monoxide in a reverse water gas shift (RWGS) reaction zone.

[0295] XVIII. A method according to any one of aspects XVII, characterized in that, according to aspect 12, the residual material (15) produced by gasification (26) is converted into carbon dioxide in combustion (27), and the optionally purified carbon dioxide is introduced into the process (6) to provide carbon monoxide.

[0296] XIX. A method according to any one of aspects XIII to XVIII, characterized in that the chlorine (8a) is provided by at least one chlorine synthesis (8), which is selected from the following chlorine synthesis

[0297] A) oxidative conversion of hydrogen chloride, which is separated from the isocyanate production (2) and purified with oxygen in a thermal catalytic gas phase oxidation to produce chlorine and water,

[0298] B) Hydrogen chloride from isocyanate production (2) is reacted with water to form hydrochloric acid, which is electrochemically oxidized to chlorine (8b) in the presence or absence of hydrogen (8a).

[0299] XX. Nitric acid as a direct process product of a nitric acid production process comprising at least the following steps:

[0300] a) Providing hydrogen (5d) and oxygen (5b) by electrolysis (5) of water in an electrolysis device using electricity (10) from renewable energy sources and using water

[0301] (5c);

[0302] b) providing ammonia (21b) in an ammonia synthesis (21) by reaction of at least nitrogen (21a) and hydrogen (5d) from the electrolysis (5) of said water;

[0303] c) producing nitric acid (22b) by reacting previously produced ammonia (21b) in the nitric acid production (22) with at least one oxygen-containing gas (5e), ​​preferably at least one oxygen-containing gas selected from the group consisting of oxygen (5b) produced by the electrolysis (5) of said water, air (24)

[0304] or oxygen (5f) from air fractionation (23);

[0305] Use for producing organic amino compounds for synthesizing organic isocyanate compounds.

[0306] XXI. A device configured to produce an organic amino compound, wherein the device comprises at least one supply for hydrogen, at least one supply for an organic nitro compound, at least one device for hydrogenating the organic nitro compound, and at least one supply of nitric acid, wherein

[0307] - at least one nitric acid supply device, comprising at least one nitric acid outlet and at least one nitric acid inlet and at least one nitric acid space;

[0308] - at least one device for producing an organic nitro compound, comprising at least one reactor, at least one inlet for an organic compound, at least one inlet for nitric acid and at least one outlet for an organic nitro compound;

[0309] - at least one hydrogenation unit for an organic nitro compound, comprising at least one reactor, at least one inlet for an organic nitro compound, at least one inlet for hydrogen and at least one outlet for an organic amino compound;

[0310] Features

[0311] i) a storage container for supplying nitric acid is filled with nitric acid, which is a direct process product of a nitric acid production process, comprising at least the following steps:

[0312] a) Providing hydrogen (5d) and oxygen (5b) by electrolysis (5) of water in an electrolysis device using electricity (10) from renewable energy sources and using water

[0313] (5c);

[0314] b) producing ammonia (21b) in an ammonia synthesis (21) by reaction of at least nitrogen (21a) and hydrogen (5d) from the electrolysis (5) of said water;

[0315] c) producing nitric acid (22b) by reacting previously produced ammonia (21b) in the nitric acid production (22) with at least one oxygen-containing gas (5e), ​​preferably at least one oxygen-containing gas selected from the group consisting of oxygen (5b) produced by the electrolysis (5) of said water, air (24)

[0316] or oxygen (5f) from air fractionation (23);

[0317] ii) a nitric acid outlet of the device for supplying nitric acid is fluidly connected to a nitric acid inlet of the device for producing organic nitro compounds;

[0318] iii) the organic nitro compound outlet of the organic nitro compound production device is fluidly connected to the organic nitro compound inlet of the organic nitro compound hydrogenation device;

[0319] iv) The hydrogen inlet of the device for hydrogenating the organic nitro compound is fluidly connected to the hydrogen outlet of the device for supplying hydrogen.

[0320] XXII. An apparatus according to aspect XXI, characterized in that the device (3) for supplying hydrogen extracts hydrogen for producing hydrogen from at least one electrolysis selected from the electrolysis of water, the electrolysis of alkali metal chlorides, the electrolysis of hydrochloric acid or two or more of the above electrolysis.

[0321] XXIII. The device according to aspect XXI or XXII, characterized in that the space for nitric acid of the device for supplying nitric acid is the space of a storage container or the space of a pipeline.

[0322] XXIV. Device according to aspect XXIII, characterized in that the space for nitric acid is a storage container and the nitric acid inlet of the device for supplying nitric acid is fluidically connected to the discharge device for the transport container.

[0323] XXV. Device according to aspect XXIII, characterized in that the space for nitric acid is a pipeline and the nitric acid inlet of the device for supplying nitric acid is fluidically connected to the outlet of the device for producing nitric acid.

[0324] XXVI. An apparatus according to any one of aspects XXI to XXV, characterized in that the outlet of the organic amino compound of the organic nitro compound hydrogenation apparatus is fluidically connected to the inlet of the organic amino compound of the phosgene apparatus, wherein the phosgene apparatus comprises at least one phosgene inlet, at least one organic amino compound inlet and at least one organic isocyanate compound outlet. Example

[0325] As material flows from the entire process, the following process parameters are obtained from the data of the individual process steps:

[0326] Example 1 - Prior Art ( Figure 7 )

[0327] Toluene diisocyanate (TDI) is prepared according to the following prior art. Figure 7 shown.

[0328] Carbon monoxide (CO) 7 and hydrogen (H2) are produced by a steam-methane reforming process 6b (SMR). For this purpose, 6.89 tons / hour of methane and 19.0 tons / hour of water from natural gas are fed to the SMR reactor 6b. In an internal loop, 3.73 tons / hour of CO2 are recovered from the process gas treatment operation 28 downstream of the SMR reactor (6). The gas leaving the SMR reactor 6b is fed to the process gas treatment operation 28 for drying, CO2 removal and CO-H2 separation. Here, a technically mature method is used. 11.36 tons / hour of carbon monoxide (CO) 7 and 2.31 tons / hour of hydrogen, 11.3 tons / hour of water, 3.73 tons / hour of CO2 and 0.92 tons / hour of tail gas containing H2, CO and unconverted methane are separated from the process gas treatment operation 28. Of the hydrogen supplied to the hydrogen supply 3, 2.15 tons / hour of hydrogen 3a are fed to the hydrogenation 20 of dinitrotoluene 19a. 0.16 t / h of hydrogen 3a from the SMR reactor 6b or its process gas treatment 28 is fed to the ammonia synthesis 21. 11.36 t / h of CO 7 is fed to the phosgene synthesis 1. CO 7 reacts here with chlorine 8b to form 35.56 t / h of phosgene 1a (COCl2). In the hydrogenation 20, 32.68 t / h of dinitrotoluene 19a reacts with 2.15 t / h of hydrogen 3a and consumes 12.93 t / h of water to form 21.91 t / h of diaminotoluene 17. Diaminotoluene 17 reacts with 35.56 t / h of phosgene 1a and consumes 26.22 t / h of hydrogen chloride to form 31.24 t / h of toluene diisocyanate 18. 16.52 t / h of toluene 19c was reacted with nitric acid 22a, calculated as 100% HNO3 and 22.62 t / h of HNO3 to obtain 32.68 t / h of dinitrotoluene 19a.

[0329] In order to produce hydrogen more efficiently, the SMR reactor (6a) is used only for the production of H2, wherein the CO produced reacts with water to produce H2 and CO2 through a water-gas shift reaction. The process uses 2.04 tons / hour of methane from natural gas and 7.78 tons / hour of water as raw materials. 0.92 tons / hour of hydrogen and 5.28 tons / hour of carbon dioxide are obtained, as well as 0.26 tons / hour of tail gas consisting of by-products such as CO, H2 and methane. In the ammonia synthesis 21, the excess hydrogen 3a produced in the SMR 6 with a hydrogen and CO production of 0.16 tons / hour is reacted with 5.03 tons / hour of N2 21a from the air fractionation 23 through the Haber-Bosch process to produce 6.10 tons / hour of ammonia 21b. Subsequently, the ammonia 21b is converted into nitric acid by combustion, that is, reacting with 22.98 tons / hour of oxygen 5f in the oxygen-containing gas 5e, and then fed to the production of dinitrotoluene 19 through the production of nitric acid 22a.

[0330] In this process, the 5.28 t / h of CO2 produced during hydrogen production is used directly in the production of NH3. The carbon in the isocyanate group in organic isocyanate 18 comes from a fossil raw material source - natural gas - and is therefore not sustainable. The carbon in the isocyanate group accounts for 22% of the carbon in TDI.

[0331] Example 2: Inventive method - overall process flow at one station ( Figure 4 )

[0332] The process steps in Example 4 are all performed at one site. In this example, Figure 4 The dashed arrows in 5a, 21b and 22a represent fluid connections for the supply of the respective materials, which may also be represented by solid lines.

[0333] The production of low-emission toluene diisocyanate (TDI) according to the invention, wherein the production of CO is converted into CO2 and H2 used as raw materials in a reforming process 6 (rWGS, reverse water gas shift reaction). Optionally, the rWGS can be heated with renewable electricity or biogas. The required hydrogen and by-product oxygen are produced by electrolysis 5 of water. The produced hydrogen is provided at 3. The hydrogen 5a produced by electrolysis of water is partly used as hydrogen 5d, which reacts with nitrogen 21a from air fractionation in ammonia synthesis 21 by the Haber-Bosch process to produce ammonia 21b. In the production of nitric acid 22, ammonia 21b reacts with air 24 or O2, optionally oxygen 5f from air fractionation 23 or oxygen 5b produced by water electrolysis 5, to produce nitric acid. The remainder of the hydrogen 5a from the electrolysis of water 5 is provided to the RWGS reformer 6 and the hydrogenation 20 of nitroaromatic compounds 19a. Renewable energy (10, 12) is used to drive the electrolysis of water 5, as well as the air fractionation 23.

[0334] 17.84 tonnes / hour of CO2 and 0.81 tonnes / hour of H2 are introduced into the rWGS reaction space (6) operated at a temperature of 802° C. The resulting product gas mixture consisting of CO 7, H2O, unconverted CO2 and unconverted H2 as well as by-products (mainly small amounts of methane) is withdrawn from the rWGS reaction 6 and sent to a process gas treatment operation (not shown) 28. In the latter, CO2 and water are separated, CO is separated from H2, and tail gas is separated.

[0335] A total of 4.04 tons / hour of hydrogen 5a and 32.32 tons / hour of oxygen 5b are extracted from the water electrolysis 5; in this case, the water electrolysis 5 is provided with 7 tons / hour of water 5c. When the water electrolysis 5 is located at the rWGS 6, isocyanate production 2, hydrogenation 20 and nitro compound production 19, NH3 synthesis 22 and HNO3 production 21, water can be separated from the hydrogenation 22, nitro compound production 21 and water electrolysis 5 and sent to the water electrolysis 5. This protects water resources and further improves the sustainability of the method of the present invention.

[0336] The gas stream drawn off from the rWGS 6 is separated in a process gas treatment operation. In this case, 11.36 t / h of CO are fed from the H2-CO separation to the phosgene synthesis 1. For this purpose, CO 7 is reacted with chlorine 8b to produce 35.56 t / h of phosgene 1a (COCl2). In the hydrogenation 20, 32.68 t / h of dinitrotoluene 19a react with 2.15 t / h of hydrogen 3a from the electrolysis (5) of water, consuming 12.93 t / h of water to form 21.91 t / h of diaminotoluene. The diaminotoluene reacts with 35.56 t / h of phosgene, eliminating 26.22 t / h of hydrogen chloride, to form 31.24 t / h of toluene diisocyanate. 16.52 t / h of toluene react with nitric acid, with 22.62 t / h of HNO3 calculated as 100% HNO3, to form 32.68 t / h of dinitrotoluene.

[0337] The electrolysis of water (5) is used to produce H2. In the electrolysis of water, 37 t / h of water are converted into 4.04 t / h of hydrogen and 32.32 t / h of oxygen. 0.81 t / h of hydrogen are fed to the rWGS (6), 1.08 t / h to the ammonia synthesis (21) and 2.15 t / h to the hydrogenation of nitro compounds (20).

[0338] The nitrogen 21a used for the production of ammonia 21b in the NH3 synthesis originates from air fractionation 23; the latter is driven by renewable energy 12. 5.03 t / h of nitrogen 21a from air fractionation 23 is fed to the ammonia synthesis 21, where it reacts with 1.08 t / h of H2 5d from the electrolysis 5 of water to produce 6.1 t / h of ammonia 21b. Ammonia is supplied from the ammonia synthesis 21 to the production of nitric acid 22 via fluid connection 21b.

[0339] In the production of nitric acid, the oxygen byproduct 5b produced by the electrolysis 5 of water can be utilized to convert 6.1 t / h of ammonia 21b into 22.6 t / h of nitric acid, calculated as 100% acid. The nitric acid is fed to the production of nitro compounds 19 via fluid connection 22a.

[0340] In this process, no direct CO2 emissions are emitted from the production of hydrogen. The carbon for the isocyanate groups comes from CO2 and is therefore introduced sustainably. As a result, 6.29 t / h of direct CO2 emissions are avoided and 22% of the carbon in the TDI is produced sustainably.

Claims

1. A method for producing an organic amino compound for synthesizing an organic isocyanate compound, comprising at least the following steps: i) providing at least one organic nitro compound (19a) as a direct process product of a process (19) for the synthesis of at least one organic nitro compound (19a), which comprises at least the following steps: i-1) providing nitric acid (22a) as a direct process product of a nitric acid production process, which comprises at least the following steps: a) providing hydrogen (5d) and oxygen (5b) by electrolysis (5) of water in an electrolysis device using electricity (10) from renewable energy sources and using water (5c); b) providing ammonia (21b) as a direct process product of the reaction of at least nitrogen (21a) and hydrogen (5d) from the electrolysis (5) of said water in an ammonia synthesis (21); c) producing nitric acid by reacting previously provided ammonia (21b) at least with an oxygen-containing gas (5e) in a nitric acid production (22); i-2) synthesizing (19) at least one organic nitro compound (19a), preferably at least one aromatic organic nitro compound (19a), by nitrating at least one organic compound (19b, 19c), preferably at least one aromatic organic compound (19b, 19c), using at least the nitric acid (22a) provided; ii) providing (3) hydrogen (3a), preferably by electrolysis of water in an electrolysis device (3b) using electricity generated from a renewable energy source (9); iii) introducing the provided at least one organic nitro compound (19a) and the provided hydrogen into a hydrogenation (20), and then hydrogenating (20) the nitro group of the at least one organic nitro compound (19a) by reduction thereof by reaction with the hydrogen (3a) to obtain at least one organic amino compound (17), preferably at least one aromatic organic amino compound (17).

2. The method according to claim 1, characterized in that The organic nitro compound (19a) is provided as a process product of the synthesis (19) in step i-2) in the form of a material flow directly from the synthesis (19) via a fluid connection, via intermediate storage - if necessary - in at least one storage container, wherein the synthesis (19), any necessary at least one storage container and the hydrogenation (20) in step iii) are fluidically connected to one another.

3. The method according to claim 1, characterized in that The organic nitro compound (19a) from step i-2) is provided as a process product of the synthesis (19) into a movable closed transport container and optionally transferred therefrom into a storage container for intermediate storage, The synthesis (19) and the hydrogenation (20) in step iii) are not fluidically connected to one another.

4. The method according to any one of claims 1 to 3, characterized in that In step i-1), nitric acid as a process product of the nitric acid production (22) is provided in the form of a material flow (22a) directly from the nitric acid production (22) via a fluid connection, via intermediate storage - if necessary - in at least one storage container, wherein the nitric acid production (22), any necessary at least one storage container and the synthesis (19) in step i-2) are fluidically connected to one another.

5. The method according to claim 4, characterized in that In step i-1), ammonia (21b) is provided as a process product of the ammonia production (21) into a movable closed transport container and optionally transferred from it into a storage container for intermediate storage, The ammonia production (21) and the nitric acid production (22) are not fluidically connected to each other.

6. The method according to any one of claims 1 to 3, characterized in that In step i-1), nitric acid as a process product of nitric acid production (22) is provided for supply (22a) into a movable closed transport container and optionally transferred from it into a storage container for intermediate storage, Wherein the nitric acid production (22) and the synthesis (19) in step ii) are not fluidically connected.

7. The method according to any one of claims 1 to 6, characterized in that The hydrogen provided in step ii) is produced by at least electrolysis (3b) of water using electrical energy (9), wherein the electrical energy (9) is supplied as a renewable energy source, optionally using wind energy, solar energy, hydroelectric power or a combination thereof.

8. The method according to any one of the preceding claims, characterized in that The organic amino compound (17) obtained in step iii) is selected from toluenediamine (TDA), methylenedianiline (MDA), (preferably selected in sequence from diphenylmethane-2,2'-diamine, diphenylmethane-2,4'-diamine, diphenylmethane-4,4'-diamine or a mixture thereof), or a mixture thereof.

9. The method according to any one of the preceding claims, characterized in that For the synthesis of organic isocyanates, at least the following steps are additionally performed: iv) synthesizing (1) phosgene (1a) from at least carbon monoxide and chlorine (8b); v) Isocyanate production (2) of an organic isocyanate (18) by reaction of at least one phosgene (1a) with at least one organic amino compound (17) with release of hydrogen chloride.

10. A method for synthesizing an organic isocyanate (18), comprising at least the following steps: Providing at least one organic nitro compound (17) as a direct process product of the process according to any one of claims 1 to 8; Synthesis (1) of phosgene (1a) from at least carbon monoxide and chlorine (8b); Isocyanate production (2) of an organic isocyanate (18) which is produced by reaction of at least one phosgene (1a) with at least one organic amino compound (17) with release of hydrogen chloride.

11. The method according to any one of claims 9 or 10, characterized in that Carbon monoxide is produced from CO2 by at least one method selected from the following: A) electrochemical reduction of carbon dioxide using electricity generated from renewable energy, B) a reforming process of converting methane and steam into carbon monoxide at a temperature of at least 500° C., with the addition of at least CO 2 and with the provision of thermal energy; C) Hydrogen and carbon dioxide are converted to carbon monoxide in a reverse water gas shift (RWGS) reaction zone.

12. Nitric acid as a direct process product of a nitric acid production process comprising at least the following steps: a) providing hydrogen (5d) and oxygen (5b) by electrolysis (5) of water in an electrolysis device using electricity (10) from renewable energy sources and using water (5c); b) providing ammonia (21b) in an ammonia synthesis (21) by reaction of at least nitrogen (21a) and hydrogen (5d) from the electrolysis (5) of said water; c) producing nitric acid (22b) by reacting previously produced ammonia (21b) in the nitric acid production (22) at least with an oxygen-containing gas (5e), ​​preferably at least one oxygen-containing gas selected from the group consisting of oxygen (5b) produced by electrolysis (5) of water, air (24) or oxygen (5f) from air fractionation (23); Use for producing organic amino compounds for synthesizing organic isocyanate compounds.

13. A device for producing organic amino compounds, wherein the device comprises at least one supply of hydrogen, at least one device for producing organic nitro compounds, at least one device for hydrogenating organic nitro compounds and at least one supply of nitric acid, wherein - at least one nitric acid supply device comprising at least one nitric acid outlet and at least one nitric acid inlet and at least one space for nitric acid; - at least one device for producing an organic nitro compound, comprising at least one reactor, at least one inlet for an organic compound, at least one inlet for nitric acid and at least one outlet for an organic nitro compound; - at least one hydrogenation unit for an organic nitro compound, comprising at least one reactor, at least one inlet for an organic nitro compound, at least one inlet for hydrogen and at least one outlet for an organic amino compound; Features i) a storage container for supplying nitric acid is filled with nitric acid, which is a direct process product of a nitric acid production process, comprising at least the following steps: a) providing hydrogen (5d) and oxygen (5b) by electrolysis (5) of water in an electrolysis device using electricity (10) from renewable energy sources and using water (5c); b) producing ammonia (21b) in an ammonia synthesis (21) by reaction of at least nitrogen (21a) and hydrogen (5d) from the electrolysis (5) of said water; c) producing nitric acid by reacting previously produced ammonia (21b) in nitric acid production (22) at least with an oxygen-containing gas (5e), ​​preferably at least one oxygen-containing gas selected from the group consisting of oxygen (5b) produced by electrolysis (5) of water, air (24) or oxygen (5f) from air fractionation (23); ii) a nitric acid outlet of the device for supplying nitric acid is fluidly connected to a nitric acid inlet of the device for producing organic nitro compounds; iii) the organic nitro compound outlet of the organic nitro compound production device is fluidly connected to the organic nitro compound inlet of the organic nitro compound hydrogenation device; iv) The hydrogen inlet of the device for hydrogenating the organic nitro compound is fluidly connected to the hydrogen outlet of the device for supplying hydrogen.

14. The device according to claim 13, characterized in that The device (3) for supplying hydrogen extracts hydrogen from at least one electrolysis for producing hydrogen, wherein the electrolysis is selected from the electrolysis of water, the electrolysis of alkali metal chlorides, the electrolysis of hydrochloric acid, or two or more of the above electrolysis.

15. The device according to claim 13 or 14, characterized in that The space for nitric acid of the apparatus for supplying nitric acid is a space of a storage container or a space of a pipe.

16. The device according to claim 13 or 14, characterized in that The space for nitric acid is the space of the storage container, and the nitric acid inlet of the device for supplying nitric acid is fluidly connected with the discharge device for the transport container.

17. The device according to claim 13 or 14, characterized in that The space for nitric acid is a pipeline, and the nitric acid inlet of the device for supplying nitric acid is fluidly connected with the outlet of the device for producing nitric acid.

18. The device according to any one of claims 13 to 17, characterized in that The outlet of the organic amino compound of the organic nitro compound hydrogenation unit is fluidly connected to the inlet of the organic amino compound of the phosgene unit, wherein the phosgene unit comprises at least one phosgene inlet, at least one organic amino compound inlet and at least one organic isocyanate compound outlet.

Images