Process for the preparation of triacetoneamine

Abstract

A process for preparing triacetoneamine, comprising the steps: a) reacting acetone and optionally acetone condensates with ammonia to give a mixture containing triacetoneamine, acetone, acetone condensates and high-boiling residues; b) fractionating the mixture obtained in step a) to obtain a fraction containing triacetoneamine, a fraction containing acetone, at least one fraction containing acetone condensates, and at least one fraction containing high-boiling residues; c) optionally recycling at least a part of the acetone and / or acetone condensates obtained in step b) into step a); d) converting the high-boiling residues obtained in step b) into propene; e) converting propene into acetone; f) recycling acetone into step a).

Description

Process for the Preparation of TriacetoneamineThe present invention concerns a process for the preparation of triacetoneamine.Triacetoneamine (2,2,6,6-tetramethylpiperidin-4-one; TAA) is one of the central building blocks for the synthesis of light stabilizers in particular for plastics and polymers, such as polyolefins (polyethylene, polypropylene, polyvinyl chloride), polyacetals and polyesters. Stabilizers of the HALS type (HALS = hindered amine light stabilizers) confer these materials improved lightfastness vis-a-vis UV radiation.TAA can be further subjected to an aminating hydrogenation to give triacetonediamine (TAD), as described e.g. in EP 0 863 137. TAD is a key intermediate for the synthesis of HALS-type light stabilizers.TAA can be prepared by reacting acetone or acetone-containing solutions of acetone follow- on products or condensation products, such as mesityl oxide, diacetone alcohol, diacetoneamine, acetonin or phorone, with ammonia in a cyclocondensation reaction.The synthesis can be carried out in one or two stages. The two-stage process is less cost- effective. In that process, the synthesis of the TAA proceeds via acetonin as an intermediate. The more cost-effective one-stage synthesis can be carried out under both homogeneous and heterogeneous catalysis. The reaction temperatures employed in this synthesis are usually within the range from 50 to 100 °C.EP-B 0 004 104 (Huis AG) discloses a process for preparing TAA which involves reacting acetone and ammonia in a molar ratio of from 2:1 to 25:1 in the presence of a solid acidic catalyst at from 80 to 130 °C under the autogenous pressure of the system, which may also be increased by adding inert gas. The solid acidic catalysts employed in this known process are virtually insoluble in both the starting materials and the reaction mixture. Catalysts which are so solid offer the advantage that their chemical stability is very high. Moreover, this known process can be carried out continuously. Nevertheless, the process is disadvantageous insofar as the yields obtained are low, being situated at about 19% based on the acetone employed.Other known TAA syntheses are conducted under batchwise conditions, resulting in increased effort and time (cf. e.g. DE-C 29 10 761 (Ciba-Geigy AG)).In the batchwise processes, various catalysts have been employed, examples being Lewis acids, Bronstedt acids, halogen compounds, etc. A common feature of all these processes is that the catalyst has, with great effort, to be separated off and removed after the reaction has been carried out. Using, for example, calcium chloride (cf. ES-A 479 049), relatively largeamounts of aqueous calcium chloride solution are obtained in the reaction, and this solution, owing to its contamination with organic substances, is difficult to eliminate.EP 0 825 182 A1 (BASF AG) discloses a process for preparing TAA that comprises reacting a mixture containing acetone and / or acetone condensates and ammonia in a molar ratio of from 20:1 to 3:1 in the presence of dimethyl sulfate at from 50 to 130 °C, the amount of dimethyl sulfate being from 0.5 to 5 mol-% based on acetone.TAA synthesis does not proceed with high selectivity (< 70%). Hence, considerable amounts of C,H,N,0 containing by-products are produced. The lower boiling by-products, such as mesityl oxide, diacetone alcohol, diacetoneamine, acetonine or phorone, can be recycled into the TAA synthesis. However higher boiling by-products, which form oil-like, wax-like or solid residues, must be disposed of.It is an object of the present invention to provide an environmentally friendly overall process for the preparation of triacetonamine (TAA). It is an object to provide a process that avoids disposal or incineration of by-products.The problem is solved by a process for preparing triacetoneamine, comprising the steps: a) reacting acetone and optionally acetone condensates with ammonia to give a mixture containing triacetoneamine, acetone, acetone condensates and high-boiling residues; b) fractionating the mixture obtained in step a) to obtain a fraction containing triacetoneamine, a fraction containing acetone, at least one fraction containing acetone condensates, and at least one fraction containing high-boiling residues; c) optionally recycling at least a part of the acetone and / or acetone condensates obtained in step b) into step a); d) converting the high-boiling residues obtained in step b) into propene; e) converting propene into acetone; f) recycling acetone into step a).By the process of the invention, disposal or incineration of the high-boiling residues can be avoided. The high-boiling residues are re-converted into acetone, which is recycled in the triacetoneamine preparation step a). The recycle loop is thereby closed. The advantage of the closed carbon cycle is that less carbon loss in a sustainable carbon-based circular economy generally means fewer CO2 emissions (= reduced Product Carbon Footprints (PCF)).In step a) of the process of the invention, acetone and optionally acetone condensates are reacted with ammonia to give a mixture containing triacetoneamine, acetone, acetone condensates and high-boiling residues. Acetone condensates are e.g. mesityl oxide, diacetone alcohol, diacetoneamine, acetonine or phorone. The reaction can be carried out as described in e.g. EP-B 0 004 104 and EP 0 825 182 A1 .In step b) of the process of the invention, the mixture obtained in step a) is fractionated to obtain a fraction containing triacetoneamine, a fraction containing acetone, at least one fraction containing acetone condensates, and at least one fraction containing high-boiling residues. Acetone condensates are e.g. mesityl oxide, diacetone alcohol, diacetoneamine, acetonine or phorone.The acetone and / or acetone condensates obtained in step b) can be, at least in part, recycled into step a). In general, recycle step c) is carried out.In step d) of the process of the invention, the high-boiling residues obtained in step b) are converted into propene by a cracking process or a pyrolysis process.In one preferred embodiment of the invention, the high-boiling residues obtained in step b) are further processed as a co-feed together with the hydrocarbon feed of a cracker (e.g. Naphtha, gas oil, LPG), and optionally together with residues from other chemical processes, in a cracking process. The cracking process can be e.g. a thermal or fluid catalytic cracking, preferably a steam cracking process, by performing cracking in the presence of steam and without the presence of oxygen (O2), to give propylene as the preferred product among others. The amount of the co-feed is preferably below 3 wt%, e.g. 0.001 to 1 .0 wt%, preferably 0.001 to 0.01 wt%, advantageously in an already existing respective plant. Typically, the reaction temperature for the steam cracking process is very high, esp. at around 750 to 900 °C, with short residence times in the cracking furnace, esp. between 1 millisecond and 1 second. The steam cracking process is described in detail by Heinz Zimmermann and Roland Walzl in Ullmann’s Encyclopedia of Industrial Chemistry, Vol. 13, Ethylene, pages 465 - 529, with further references.In another embodiment of the invention, the high-boiling residues obtained in step b) are further processed by a pyrolysis process to give propylene as the preferred product among others. The high-boiling residues obtained in step b) can be the sole feed of a pyrolysis unit. Preferably the high-boiling residues obtained in step b) are converted as a co-feed together with the feed of a pyrolysis unit into propene by the pyrolysis process. In a specific embodiment, the high-boiling residues obtained in step b) are used as a co-feed together with one or more other feeds (e.g. residues from other chemical processes, carbonaceous materials, plastic waste), advantageously in an already existing respective plant. The amount of the cofeed is preferably below 10 wt%, e.g. 1 .0 to 5.0 wt%.Pyrolysis is one of the various types of chemical degradation processes that occur at higher temperatures (above the boiling point of water or other solvents). It differs from other processes like combustion and hydrolysis in that it usually does not involve the addition of other reagents such as oxygen (O2, in combustion) or water (in hydrolysis). Pyrolysis produces solids (char), condensable liquids, (light and heavy oils and tar), and non-condensable gasses (see e.g. WO 2024 / 083776 A1 (BASF SE)).Pyrolysis is different from gasification. Pyrolysis refers to a partial thermal degradation of carbonaceous materials that takes place in an inert [oxygen (O2) free, at least essentially oxygen (O2) free] atmosphere and produces both gases, liquids and solids. The pyrolysis can be extended to full gasification that produces mainly gaseous output, often with the addition of e.g. water steam to gasify residual carbonic solids (Steam reforming).The thermal energy necessary for the cracking process or the pyrolysis process is provided at least in part by electrical power generated at least in part from non-fossil, renewable resources. In other words, part of the electrical power can still be produced from fossil fuels, preferably from natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of electrical energy produced than combustion of coal. However, the portion of electrical energy produced from fossil fuels should be as low as possible, preferably < 50%, preferably < 30%, most preferably < 20%.The electrical power from non-fossil resources used in water electrolysis according to the invention can be generated by nuclear energy. Nuclear energy is considered renewable by the European Commission, as long as certain preconditions (i. a. safe long-term storage of nuclear waste) are fulfilled.The electrical power from non-fossil resources used in water electrolysis according to the invention is preferably generated from wind power, solar energy, biomass, hydropower and geothermal energy.In one preferred embodiment of the inventive process, the electrical power used in water electrolysis is generated from hydropower. There are many forms of hydropower. Traditionally, hydroelectric power comes from constructing large hydroelectric dams and reservoirs. Small hydro systems are hydroelectric power installations that typically produce up to 50 MW of power. They are often used on small rivers or as a low-impact development on larger rivers. Run-of-the-river hydroelectricity plants derive energy from rivers without the creation of a large reservoir. The water is typically conveyed along the side of the river valley (using channels, pipes and / or tunnels) until it is high above the valley floor, whereupon it can be allowed to fall through a penstock to drive a turbine.Wave power, which captures the energy of ocean surface waves, and tidal power, converting the energy of tides, are two forms of hydropower with future potential.In one further preferred embodiment of the inventive process, the electrical power used in electrolysis is generated at least in part from geothermal energy. Geothermal energy is the heat that comes from the sub-surface of the earth. It is contained in the rocks and fluids beneath the earth’s crust and can be found as far down to the earth’s hot molten rock, magma.To produce power from geothermal energy, wells are dug a mile deep into underground reservoirs to access the steam and hot water there, which can then be used to drive turbines connected to electricity generators. There are three types of geothermal power plants; dry steam, flash and binary. Dry steam is the oldest form of geothermal technology and takes steam out of the ground and uses it to directly drive a turbine. Flash plants use high-pressure hot water into cool, low-pressure water whilst binary plants pass hot water through a secondary liquid with a lower boiling point, which turns to vapor to drive the turbine.In one further preferred embodiment of the inventive process, the electrical power used in water electrolysis is generated from wind power. Wind power can be used to run wind turbines. Modern utility-scale wind turbines range from around 600 kW to 9 MW of rated power. The power available from the wind is a function of the cube of the wind speed, so as wind speed increases, power output increases up to the maximum output for the particular turbine. Areas where winds are stronger and more constant, such as offshore and high-altitude sites, are preferred locations for wind farms.In one further preferred embodiment of the inventive process, the electrical power used in water electrolysis is generated from solar power, particularly preferred from photovoltaic systems. A photovoltaic system converts light into electrical direct current (DC) by taking advantage of the photoelectric effect. Concentrated solar power (CSP) systems use lenses or mirrors and tracking systems to focus a large area of sunlight into a small beam. CSP-Stirling has by far the highest efficiency among all solar energy technologies.In one further preferred embodiment of the inventive process, the electrical power used in water electrolysis is generated from biomass. Biomass is biological material derived from living, or recently living organisms. It most often refers to plants or plant-derived materials which are specifically called lignocellulosic biomass. As an energy source, biomass can either be used directly via combustion to produce heat or electricity, or indirectly after converting it to various forms of biofuel. Conversion of biomass to biofuel can be achieved by different methods which are broadly classified into: thermal, chemical, and biochemical methods. Wood was the largest biomass energy source as of 2012; examples include forest residues - such as dead trees, branches and tree stumps -, yard clippings, wood chips and even municipal solid waste. Industrial biomass can be grown from numerous types of plants, including miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, bamboo, and a variety of tree species, ranging from eucalyptus to oil palm (palm oil).In one preferred embodiment of the process of the invention, in step d), the high-boiling residues are converted into propene by a process comprising the steps: d1) converting the high-boiling residues into synthesis gas containing carbon monoxide and hydrogen; d2) optionally admixing hydrogen, preferably produced by water electrolysis, to the synthesis gas obtained in step d1);d3) reacting the synthesis gas obtained in step d1) or d2) to give methanol; d4) manufacturing C2-C4-olefins including propene by a methanol to olefin-process from methanol obtained in step d3).In step d3) of the process of the invention, a gas mixture containing carbon monoxide, hydrogen and optionally carbon dioxide obtained in step d1 ) or d2) is reacted to give methanol.The current world-scale technology for methanol synthesis is mostly based on the application of Cu / ZnO / AI2O3(CZA) catalysts in either multi-tube reactors with boiling water as the cooling fluid, normally called isothermal reactors (e.g., the Lurgi process, the Linde process), or adiabatic reactors with intermediate cold syngas quenching, generally named quench reactors (e.g., ICI and the Casale process, the Haldor Topsoe process). Less common but also industrially applied are the adiabatic reactors with intermediate cooling (e.g., the Kellogg process, the Toyo process). Normally, temperatures between 200 and 300 °C and pressures between 50 and 100 bar (abs) are applied. See Bozzano, G.; Manenti, F. Efficient methanol synthesis: Perspectives, technologies and optimization strategies. Prog. Energy Combust. Sci. 2016, 56, 71-105; and Ott, J.; Gronemann, V.; Pontzen, F.; Fiedler, E.; Grossmann, G.; Kerse- bohm, D.B.; Weiss, G.; Witte, C. Methanol. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley: New York, NY, USA, 2012.In step d4) of the process of the invention, C2-C4-olefins including propylene are manufactured by a methanol to olefin-process (MTO-process) from methanol obtained in step d3). See e.g. ACS Catal. 2015, 5, 1922-1938, DOI: 10.1021 / acscatal.5b00007; and WO 2024 / 056428 A1 , WO 2024 / 153677 A1 (both BASF SE).C2-C4-olefins different from propylene (ethylene, 1 -butene, 2-butene (cis / trans), isobutene) can be further reacted via a metathesis reaction to give propylene, as described in e.g. EP 0 915 072 A1 (BASF AG).In an alternative process of the invention, in step d), the high-boiling residues are converted into propene by a process comprising the steps: dT) converting the high-boiling residues into synthesis gas containing carbon monoxide and hydrogen; d2’) optionally admixing hydrogen, preferably produced by water electrolysis, to the synthesis gas obtained in step dT); d3’) reacting the synthesis gas obtained in step dT) or d2’) in a Fischer-Tropsch synthesis to give olefins including propene.If hydrogen is admixed in step d2) and d2’), respectively, it is preferably produced by water electrolysis using electrical power generated at least in part from non-fossil, renewable resources, as detailed above.In preferred embodiments of the process of the invention, in step d1) and d1 ’), respectively, the high-boiling residues are converted into synthesis gas by a gasification process or a partial oxidation process. It is preferred to use the high-boiling residues obtained in step b) as a co-feed together with other feeds (e.g. residues from other chemical processes, carbonaceous materials, plastic waste, pyrolysis oil from the pyrolysis of plastic waste), advantageously in an already existing respective plant. The amount of the co-feed is preferably below 20 wt%, more preferably below 10 wt%, e.g. 0,5 to 8.0 wt%.Partial oxidation (POX) is a type of chemical reaction. It occurs when a substoichiometric fuel-air mixture is partially combusted in a reformer, creating a hydrogen-rich syngas. Partial oxidation is a technically mature process in which natural gas or a heavy hydrocarbon fuel is mixed with a limited amount of oxygen (O2) in an exothermic process, following the general reaction equation:Water may be added to lower the combustion temperature and reduce soot formation. Yields are below stoichiometric due to some fuel being fully combusted to carbon dioxide and water.Gasification is a process that converts biomass- or fossil fuel-based carbonaceous materials into gases, including as the largest fractions: nitrogen (N2), carbon monoxide (CO), hydrogen (H2), and carbon dioxide (CO2). This is achieved by reacting the feedstock material at high temperatures (typically >700 °C), without combustion, via controlling the amount of oxygen (O2) and / or steam present in the reaction. The resulting gas mixture is synthesis gas (syngas, a mixture of CO and H2).Suitable gasifiers comprise counter-current fixed bed reactors, co-current-fixed bed reactors, bubbling fluidized bed reactors, circulating fluidized bed reactors, and downdraft or updraft entrained flow reactors. The selection of size and reactor type depends on several parameters, including the composition of the feedstock, demand of products, moisture content and availability of the feedstock. Preferably, the gasifier is an „oxygen blown" gasifier, i.e., oxygen is preferably used as the oxidant in suitable gasifiers listed above. Another preferred type of gasifiers are plasma gasifiers, particularly fixed-bed plasma gasifiers. The electrical power required for generation of the plasma is most preferably provided from renewable energy sources such as solar energy, wind energy and tidal energy.The gasification reaction in a gasifier is typically carried out at a temperature > 700 °C in the presence of a sub-stoichiometric amount of an oxidant such as oxygen, air, steam, supercritical water, CO2, or a mixture of the aforementioned. Oxygen is the most common oxidant used for gasification because of its easy availability and low cost. If steam acts as oxidant, the syngas has a higher first molar ratio H2 : CO than in case if air is used as oxidant. For example, a typical molar ratio “air : combined feedstock” ranges from 0.3 to < 1 . CO2 whenused is preferably provided by a carbon capture process such as separation of CO2 from syngas by an absorption or adsorption process during syngas purification.The conversion of a feedstock in the gasifier produces a syngas which consists primarily of H2, CO, CO2, methane, other hydrocarbons, and impurities. Said syngas has a dedicated molar ratio H2 : CO when leaving the gasifier which ranges from about 0.1 : 1 to about 3 : 1 and depends on the type of solid and / or liquid feedstocks used, the oxidant and other reaction conditions applied such as temperature and / or residence time of the reactants in the gasifier.The thermal energy necessary for the gasification process or the partial oxidation process (POX) is preferably provided at least in part by electrical power generated at least in part from non-fossil, renewable resources, as detailed above.Preferably, oxygen produced by water electrolysis is added in the gasification process or the partial oxidation process.In step d3’) the synthesis gas obtained in step dT) or d2’) is reacted in a Fischer-Tropsch synthesis to give olefins including propene.The Fischer-Tropsch synthesis offers a wide ranging distribution of hydrocarbons. For cobalt catalysts with manganese as a promoter, a high selectivity to olefins is found for the low-temperature Fischer-Tropsch synthesis. See D. Schroder et al., CataL Sci. TechnoL, 2020,10, 475-483.In step e) of the process of the invention, propene is converted into acetone.Acetone is produced directly or indirectly from propene. Most of the acetone is produced via the cumene process. As a result, acetone production is tied to phenol production. In the cumene process, benzene is alkylated with propylene to produce cumene, which is oxidized by air to produce phenol and acetone:Other processes involve the direct oxidation of propylene (Wacker-Hoechst process), or the hydration of propylene to give 2-propanol, which is oxidized (dehydrogenated) to acetone.In one embodiment of the process of the invention, in step e), propene is converted into acetone bye1 ) alkylating benzene with propene to give cumene, and e2) oxidation of cumene via cumene hydroperoxide to give phenol and acetone.In another embodiment of the process of the invention, in step e), propene is converted into acetone by e1 ’) hydrating propene to give isopropanol, and e2’) oxidation of isopropanol to give acetone.Preferably, oxygen produced by water electrolysis is used in oxidation step e2) and e2’), respectively. More preferably, the electrical power used in water electrolysis is generated at least in part from non-fossil, renewable resources, as detailed above.In a preferred embodiment, step d) is: d) converting the high-boiling residues obtained in step b) into propene and further chemical material.In a further embodiment, the process, as described herein, comprises the step: converting the further chemical material obtained by or obtainable by the process described herein to obtain a product PRF1.In a preferred embodiment, the product PRF1 is selected from: i) building block or monomer; or ii) polymer, preferably polymer A, polymer composition, preferably polymer compositionA, or polymer product, preferably polymer product A; or iii) industrial use polymer, industrial use surfactant, descaling compound, industrial use biocide, industrial use solvent, industrial use dispersant, composition thereof or formulation thereof; or iv) agrochemical composition, agrochemical formulation auxiliary or agrochemically active ingredient; or v) active pharmaceutical ingredient or intermediate thereof, pharmaceutical excipient, animal feed additive, human food additive, dietary supplements, aroma chemical or aroma composition; or vi) aqueous polymer dispersion, preferably polyurethane or polyurethane - poly(meth)acrylate hybrid polymer dispersion, emulsion, binder for paper and fiber coatings, UV-curable acrylic polymer for hot melts and coatings polyisocyanates, hyperbranched polyester polyol, polymeric dispersant for inorganic binder compositions, unsaturated polyester polyol or 100% curable composition; or vii) cosmetic surfactant, emollient, wax, cosmetic polymer, UV filter, further cosmetic ingredient or composition or formulation thereof; or viii) polymer B, polymer composition B, coating composition, other functional composition, foil, molded body, coating or coated substrate.In a preferred embodiment, the content of the high-boiling residues in the product PRF1 is 1 weight-% or more, preferably 2 weight-% or more, more preferably 5 weight-% or more, more preferably 15 weight-% or more, more preferably 30 weight-% or more, more preferably 40 weight-% or more, more preferably 60 weight-% or more, more preferably 80 weight-% or more, more preferably 90 weight-% or more, more preferably 95 weight-% or more; and / or the content of the high-boiling residues in the product PRF1 is 100 weight-% or less, preferably 95 weight-% or less, more preferably 90 weight-% or less, more preferably 50 weight-% or less, more preferably 25 weight-% or less, more preferably 10 weight-% or less; and preferably wherein the content is determined based on identity preservation and / or segregation and / or mass balance and / or book and claim chain of custody models, preferably based on mass balance, preferably the International Sustainability and Carbon Certification (ISCC) standard.The publication Prior Art Disclosure; Issue 684; paragraphs

[1000] to

[8005] ; ISSN: 2198- 4786; published: February 12, 2024 will be regarded as Reference RF1 , which is incorporated herein by reference in its entirety. Preferably, the product PRF1 is a product as described in Reference RF1 ; paragraphs

[1000] to

[8005] , Preferably, the process described herein is further a process for the production of a product, preferably product PRF1 .The converting step to obtain the product PRF1 preferably comprises one or more step(s) as described below and can be performed by conventional methods well known to a person skilled in the art. The converting step preferably comprises one or more step(s) selected from: recycling, preferably depolymerizing, gasifying, pyrolyzing, and / or steam cracking; and / or purifying, preferably crystallizing, (solvent) extracting, distilling, evaporating, hydrotreating, absorbing, adsorbing and / or subjecting to ion exchanger; and / or assembling, preferably foaming, synthesizing, chemical conversion, chemically transforming, polymerizing and / or compounding; and / or forming, preferably foaming, extruding and / or molding; and / or finishing, preferably coating and / or smoothing.In addition, the one or more step(s) are described in detail in Reference RF1 ; paragraphs

[1000] to

[8005] ,The term “building block”, as used herein, comprises compounds, which are in a gaseous or liquid state under standard conditions of 0°C and 0.1 MPa. Building blocks are typically used in chemical industry to form secondary products, which provide a higher structural complexity and / or higher molecular weight than the building block on which the secondary product is based. The building block is preferably selected from the group consisting of hydrogen, carbon monoxide, carbon dioxide, ethylene oxide, ethylene glycols, syngas comprising a mixture of hydrogen and carbon monoxide, alkanes, alkenes, alkynes and aromatic compounds. The alkanes, alkenes, alkynes and aromatic compounds comprise in particular 1 to 12 carbon atoms, respectively.The term “monomer”, as used herein, comprises molecules, which can react with each other to form polymer chains by polymerization. The monomer is preferably selected from the group consisting of (meth)acrylic acid, salts of (meth)acrylic acid; in particular sodium, potassium and zinc salts; (meth)acrolein and (meth)acrylates. (Meth)acrylates comprising 1 to 22 carbon atoms are preferred, in particular comprising 1 to 8 carbon atoms. The terms (meth)acrylic acid, (meth)acrolein or (meth)acrylate relate to acrylic acid, acrolein or acrylate and also to methacrylic acid, methacrolein or methacrylate, where applicable. Further, the monomer can be selected from hexamethylenediamine (HMD) and adipic acid.The building block can further be an intermediate compound. The term “intermediate compound”, as used herein, comprises organic reagents, which are applied for formation of compounds with higher molecular complexity. The intermediate compound can be selected for example from the group consisting of phosgene, polyisocyanates and propylene oxide. The polyisocyanates are in particular aromatic di- and polyisocyanates, preferably toluene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI).The building block and the monomer and typical converting step(s) to obtain the building block or monomer are described in more detail in paragraphs

[1000] to

[1012] of Reference RF1.The term “polymer A”, as used herein, comprises thermoplastic, e.g., polyamide or thermoplastic polyurethane, thermoset, e.g., polyurethane, elastomer, e.g., polybutadiene, or a copolymer or a mixture thereof and is defined in more detail in paragraphs

[2001] to

[2007] of Reference RF1.The term “polymer composition A”, as used herein, comprises all compositions comprising a polymer as described above and one or more additive(s), e.g. reinforcement, colorant, modifier and / or flame retardant, and is defined in more detail in paragraph

[2008] of Reference RF1.The term “polymer product A”, as used herein, comprises any product comprising the polymer A and / or polymer composition A as described above and is defined in more detail in paragraphs

[2009] and

[2010] of Reference RF1 .The step(s) to obtain the polymer, preferably polymer A, polymer composition, preferably polymer composition A or polymer product, preferably polymer product A is / are described in more detail in paragraph

[2011] of Reference RF1.The term “industrial use polymer”, as used herein, comprises rheology, polycarboxylate, alkoxylated polyalkylenamine, alkoxylated polyalkylenimine, polyether-based, dye inhibition and soil release cleaning polymers defined in more detail in paragraphs

[3035] to

[3044] ofReference RF1. The term “industrial use surfactant”, as used herein, comprises non-ionic, anionic and amphoteric industrial use surfactants defined in more detail in paragraphs

[3008] to

[3034] of Reference RF1 . The term “industrial use descaling compound”, as used herein, comprises non-phosphate based builders (NPB) and phosphonates (CoP) described in more detail in paragraphs

[3001] to

[3005] of Reference RF1 . The term “industrial use biocide”, as used herein, refers to a chemical compound that kills microorganisms or inhibits their growth or reproduction defined in more detail in paragraphs

[3006] to

[3007] of Reference RF1 . The term “industrial use solvent”, as used herein, comprises alkyl amides, alkyl lactamides, alkyl esters, lactate esters, alkyl diester, cyclic alkyl diester, cyclic carbonates, aromatic aldehydes and aromatic esters defined in more detail in paragraphs

[3045] to

[3055] of Reference RF1 . The term “industrial use dispersant”, as used herein, comprises anionic and non-ionic industrial use dispersants defined in more detail in paragraphs

[3056] to

[3058] of Reference RF1 . The term “composition and / or formulation thereof’ with reference to the industrial use polymers, industrial use surfactants, descaling compounds and / or industrial use biocides refers to industrial use compositions and / or institutional use products and / or fabric and home care products and / or personal care products defined in more detail in paragraph

[3059] of Reference RF1. The converting step(s) to obtain the industrial use polymer, industrial use surfactant, descaling compound and / or industrial use biocide are defined in more detail in paragraph

[3060] of Reference RF1. The converting steps to obtain the industrial use composition or formulation of the industrial use polymer, industrial use surfactant, descaling compound and / or industrial use biocide are defined in more detail in paragraph

[3061] of Reference RF1.The term “agrochemical composition”, as used herein, typically relates to a composition comprising an agrochemically active ingredient and at least one agrochemical formulation auxiliary. Examples of agrochemical compositions, active ingredients and auxiliaries are described in more detail in Reference RF1 , paragraph

[4001] ,The agrochemical composition may take the form of any customary formulation. The agrochemical compositions are prepared in a known manner, e.g. described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. The converting step(s) to obtain the agrochemically active ingredients and auxiliaries may be conducted in analogy to the production step(s) of their analogues that are based on petrochemicals or other precursors that are not gained by recycling processes. In addition, conversion to compounds mentioned in sections “Polymer” and “Cosmetic surfactant, emollient, wax, cosmetic polymer, UV filter, further cosmetic ingredient or compositions or formulations thereof’ may be performed as described in these sections as well as the respective paragraphs in Reference RF1.The term active pharmaceutical ingredients and / or intermediates thereof, as used herein, comprises substances that provide pharmacological activity or other direct effect in the diagnosis, cure, mitigation, treatment, or prevention of disease, or to affect the structure or any function of the body. Intermediates thereof are isolated products that are generated during a multi-step route of synthesis of an active pharmaceutical ingredient. The term pharmaceutical excipients, as used herein, comprises compounds or compound mixtures used in compositions for various pharmaceutical applications, which are not substantially pharmaceutically active on itself. Active pharmaceutical ingredients and / or intermediates thereof and pharmaceutical excipients are defined in more detail in paragraph

[5001] of Reference RF1.The converting step(s) to obtain the active pharmaceutical ingredients and / or intermediates thereof and pharmaceutical excipients may comprise one or more synthesis steps and can be performed by conventional synthesis and techniques well known to a person skilled in the art.The terms animal feed additives, human food additives, dietary supplements, as used herein, comprises Vitamins, Pro-Vitamins and active metabolites thereof including intermediates and precursors, especially Vitamin A, B, E, D, K and esters thereof, like acetate, propionate, palmitate esters or alcohols thereof like retinol or salts thereof and any combinations thereof; Tetraterpenes, especially isoprenoids like carotenoids and xanthophylls including their intermediates and precursors as well as mixtures and derivates thereof, especially beta carotene, Canthaxanthin, Citranaxanthin, Astaxanthin, Zeaxanthin, Lutein, Lycopene, Apo-carotenoids, and any combinations thereof; organic acids, especially formic acid, propionic acid and salts thereof, such as sodium, calcium or ammonium salts, and any combinations thereof, such as but not limited to mixtures of formic acid and sodium formiate, propionic acid and ammonium propionate, formic acid and propionic acid, formic acid and sodium formiate and propionic acid, propionic acid and sodium propionate and formic acid and sodium formiate; glycerides of carboxylic acids and short and medium chain fatty acids, conjugated linoleic acids, such as omega-6 fatty acid (C18:2) methyl ester and 1 ,2-propandiol and beverage stabilizers, such as polyvinylpyrrolidone-polymer or polyvinylimidazole / polyvinylpyrrolidone-copolymer. Animal feed additives, human food additives and dietary supplements are defined in more detail in paragraph

[5002] of Reference RF1.The converting step(s) to obtain the animal feed additives, human food additives, dietary supplements may comprise one or more synthesis steps and can be performed by conventional synthesis and techniques well known to a person skilled in the art.The terms aroma chemical and aroma composition as used herein, comprise a volatile organic substance with a molecular weight between 70-250 g / mol comprising a functional group with a carbon skeleton of C5-C16 carbon atoms comprising linear, branched, cyclic, for example with a ring size of C5-C18, bicyclic or tricyclic aliphatic chains and but not necessarily one or more unsaturated structural elements like double bonds, triple bonds, aromatics or heteroaromatics and preferably the one or more additional functional groups are selectedfrom alcohol, ether, ester, ketone, aldehyde, acetal, carboxylic acid, nitrile, thiol, amine. In one aspect, the aroma chemical is a terpene-based aroma chemical, for example selected from monoterpenes and monoterpenoids, sesquiterpenes and sesquiterpenoids, diterpenes, triterpenes or tetraterpenes. Aroma chemicals can be combined with further aroma chemicals to give an aroma composition. Aroma chemicals and aroma compositions are defined in more detail in paragraph

[5003] of Reference RF1.The converting step(s) to obtain the aroma chemical and aroma composition may comprise one or more synthesis steps and can be performed by conventional synthesis and techniques well known to a person skilled in the art.The term “aqueous polymer dispersion”, as used herein, comprises aqueous composition(s) comprising dispersed polymer(s) and is defined in more detail in the section

[6001] entitled “aqueous polymer dispersion” of Reference RF1 . The dispersed polymer(s) may be selected from acrylic emulsion polymer(s), styrene acrylic emulsion polymer(s), styrene butadiene dispersions), aqueous dispersion(s) comprising composite particles, acrylate alkyd hybrid dispersions), polyurethane(s) (including UV-curable polyurethanes) and polyurethane - poly(meth)acrylate hybrid polymer(s). The term “emulsion polymer”, as used herein, comprises polymer(s) made by free-radical emulsion polymerization. Aqueous polyurethane dispersions) are defined in more detail in the section

[6002] entitled “Polyurethane dispersions” of Reference RF1. UV-curable polyurethane(s) is / are defined in more detail in the section

[6017] of Reference RF1. Polyurethane - poly(meth)acrylate hybrid polymer(s) is / are defined in more detail in the section

[6016] of Reference RF1 .The term “polymeric dispersant”, as used herein, comprises preferably polymer(s) comprising polyether side chain, in particular polycarboxylate ether polymer(s) and polycondensation product(s) defined in more detail in paragraph

[6020] entitled “Polymeric dispersant” of Reference RF1.The converting (polymerization) step(s) to obtain the aqueous polymer dispersion(s) comprising emulsion polymer(s) is / are defined in more detail in the section

[6003] entitled “Emulsion polymerization” of Reference RF1 .The converting (polymerization) step(s) to obtain the aqueous polyurethane dispersion(s) is / are defined in more detail in the section

[6014] entitled “Process for the preparation of aqueous polyurethane dispersions” and section

[6017] entitled “Aqueous UV-curable polyurethane dispersions, their preparation and use and compositions containing them” of Reference RF1.Composition(s) and uses of aqueous polymer dispersion(s) and of polymeric dispersant(s) are defined in more detail in the following sections of Reference RF1 : section

[6004] entitled “Uses of aqueous polymer dispersions”,section

[6005] entitled “Binders for architectural and construction coatings” section

[6006] entitled “Binders for paper coating” section

[6007] entitled “Binders for fiber bonding” section

[6008] entitled “Adhesive polymers and adhesive compositions” section

[6015] entitled “Aqueous polyurethane dispersions suitable for use in coating compositions” section

[6016] entitled “Aqueous polyurethane - poly(meth)acrylate hybride polymer dispersions suitable for use in coating compositions” section

[6017] entitled “Aqueous UV-curable polyurethane dispersions, their preparation and use and compositions containing them” section

[6018] entitled “Inorganic binder compositions comprising polymeric dispersants and their use”

[6019] 100% curable coating compositionsUV-crosslinkable poly(meth)acrylate(s) and its / their uses are defined in more detail in section

[6009] entitled “UV-crosslinkable poly(meth)acrylates for use in UV-curable solvent-free hot- melt adhesives and their use for making pressure-sensitive self-adhesive articles” of Reference RF1.Polyisocyanate(s), composition(s) comprising them and their uses are defined in more detail in section

[6010] entitled “Polyisocyanates” of Reference RF1 .Hyperbranched polyester polyol(s) and its / their uses are defined in more detail in section

[6011] entitled “Organic solvent based hyperbranched polyester polyols suitable for use in coating compositions” of Reference RF1. The converting step(s) to obtain the hyperbranched polyester polyols is / are defined in more detail in the section

[6012] entitled “Preparation of organic solvent based hyperbranched polyester polyols” of Reference RF1 . Coating compositions) comprising hyperbranched polyester polyol(s), polyisocyanate(s) and additive(s) and substrate(s) coated therewith are defined in more detail in section

[6013] entitled “Organic solvent based two component coating compositions comprising hyperbranched polyester polyols and polyisocyanates” of Reference RF1 .Unsaturated polyester polyol(s), solvent-based coating composition(s) comprising said unsaturated polyester polyol(s) and substrate(s) for coating with said coating composition(s) are defined in more detail in section

[6018] entitled “Organic solvent based coating composition comprising unsaturated polyester polyols” of Reference RF1.100% curable coating composition(s) is / are defined in more detail in section

[6019] of Reference RF1.Polymeric dispersant(s) for inorganic binder compositions is / are defined in more detail in section

[6020] of Reference RF1 . The inorganic binder composition(s) comprising the polymeric dispersants and their use are defined in more detail in section

[6021] of Reference RF1 . Theconverting step(s) to obtain the polymeric dispersant(s) are defined in more detail in section

[6020] of Reference RF1 . The term “inorganic binder composition” comprising the polymeric dispersant(s), as used herein, comprises preferably in particular hydraulically setting compositions and compositions comprising calcium sulfate and is defined in more detail in section

[6021] of Reference RF1 entitled “Inorganic binder compositions comprising the polymeric dispersant and their use”. Specific building material formulation(s) comprising polymeric dispersants) or building product(s) produced by a building material formulation comprising a polymeric dispersant are disclosed in more detail in section

[6021] of Reference RF1 .The term “cosmetic surfactant”, as used herein, comprises non-ionic, anionic, cationic and amphoteric surfactants and is defined in more detail in paragraph

[7002] of Reference RF1 . The term “emollient”, as used herein, refers to a chemical compound used for protecting, moisturizing, and / or lubricating the skin and is defined in more detail in paragraph

[7003] of Reference RF1. The term “wax”, as used herein, comprises pearlizers and opacifiers and is defined in more detail in paragraph

[7004] of Reference RF1 . The term “cosmetic polymer”, as used herein, comprises any polymer that can be used as an ingredient in a cosmetic formulation and is defined in more detail in paragraph

[7005] of Reference RF1 . The term “UV filter”, as used herein, refers to a chemical compound that blocks or absorbs ultraviolet light and is defined in more detail in paragraph

[7006] of Reference RF1 . The term “further cosmetic ingredient”, as used herein, comprises any ingredient suitable for making a cosmetic formulation. Several sources disclose cosmetically acceptable ingredients. E. g. the database Cosing on the internet pages of the European Commission discloses cosmetic ingredients and the International Cosmetic Ingredient Dictionary and Handbook, edited by the Personal Care Products Council (PCPC), discloses cosmetic ingredients. The term “composition and / or formulation thereof’ with reference to the cosmetic surfactant, emollient, wax, cosmetic polymer, UV filter and / or further cosmetic ingredient refers to personal care and / or cosmetic compositions or formulations defined in more detail in paragraph

[7007] of Reference RF1 . The converting step(s) to obtain the cosmetic surfactant, emollient, wax, cosmetic polymer, UV filter or further cosmetic ingredient is / are defined in more detail in paragraph

[7008] of Reference RF1.The terms “polymer B”, “polymer composition B”, “coating composition”, “other functional composition”, “foil”, “molded body”, “coating” and “coated substrate” are well known to the person skilled in the art and are defined in more detail from paragraph

[8000] to

[8005] of Reference RF1.ExamplePreparation of Triacetoneamine (TAA)As described in EP 4104 B1 , example 6, in a first step acetone is continuously reacted with ammonia in a cylindrical reactor at 100 °C and 70 bar using Lewatit® SP 120 as solid catalyst. The obtained reaction mixture consists of 50 wt% acetone, 5 wt% water, 13 wt% TAA, 24 wt% by-products (mesityl oxide, diacetone alcohol, diacetone amine, acetonine, phorone) with a boiling point lower than TAA, and 8 wt% by-products with a boiling point higher than TAA. Fractionated distillation delivers the desired product TAA, unreacted acetone, the lower boiling by-products, and, as the distillation residue, the higher boiling by-products in form of a dark red-brown oil (at 100°C). The acetone and the lower boiling by-products are recycled into the first step. The destination residue is mixed with naphtha, resulting in a naphtha solution containing 0.005 wt% of the residue-oil. This naphtha solution is used in a steam cracker as feed for a steam cracking process, by performing cracking in the presence of steam and without the presence of oxygen (O2), to give propylene as the preferred product among other valuable unsaturated hydrocarbons. The reaction temperature for the steam cracking process is around 750 to 900 °C, with short residence times in the cracking furnace at around 300 to 700 milliseconds. A portion of the obtained propene is directly oxidized using oxygen in the presence of a PdCh-containing catalyst-system at 115 °C and 12 bar (Wacker-Hoechst process) to give acetone in 91 % yield. The obtained acetone is recycled into the first step.

Claims

Patent claims1 . A process for preparing triacetoneamine, comprising the steps: a) reacting acetone and optionally acetone condensates with ammonia to give a mixture containing triacetoneamine, acetone, acetone condensates and high-boiling residues; b) fractionating the mixture obtained in step a) to obtain a fraction containing triacetoneamine, a fraction containing acetone, at least one fraction containing acetone condensates, and at least one fraction containing high-boiling residues; c) optionally recycling at least a part of the acetone and / or acetone condensates obtained in step b) into step a); d) converting the high-boiling residues obtained in step b) into propene; e) converting propene into acetone; f) recycling acetone into step a).

2. The process according to claim 1 , wherein, in step d), the high-boiling residues obtained in step b) are converted into propene by a cracking process or a pyrolysis process.

3. The process according to claim 2, wherein the high-boiling residues obtained in step b) are converted as a co-feed together with the hydrocarbon feed of a cracker into propene by a cracking process.

4. The process according to claim 2, wherein the high-boiling residues obtained in step b) are converted as a co-feed together with the feed of a pyrolysis unit into propene by a pyrolysis process.

5. The process according to claim 2 or 3, wherein, in step d), the high-boiling residues obtained in step b) are converted into propene by a steam cracking process.

6. The process according to any one of claims 2 to 5, wherein the thermal energy necessary for the cracking process or the pyrolysis process is provided at least in part by electrical power generated at least in part from non-fossil, renewable resources.

7. The process according to claim 1 , wherein, in step d), the high-boiling residues are converted into propene by a process comprising the steps: d1 ) converting the high-boiling residues into synthesis gas containing carbon monoxide and hydrogen; d2) optionally admixing hydrogen, preferably produced by water electrolysis, to the synthesis gas obtained in step d1 ); d3) reacting the synthesis gas obtained in step d1) or d2) to give methanol; d4) manufacturing C2-C4-olefins including propene by a methanol to olefin-process from methanol obtained in step d3).

8. The process according to claim 1 , wherein, in step d), the high-boiling residues are converted into propene by a process comprising the steps: dT) converting the high-boiling residues into synthesis gas containing carbon monoxide and hydrogen; d2’) optionally admixing hydrogen, preferably produced by water electrolysis, to the synthesis gas obtained in step dT); d3’) reacting the synthesis gas obtained in step dT) or d2’) in a Fischer-Tropsch synthesis to give olefins including propene.

9. The process according to claim 7 or 8, wherein the high-boiling residues obtained in step b) are converted as a co-feed together with other feeds into synthesis gas containing carbon monoxide and hydrogen.

10. The process according to any one of claims 7 to 9, wherein the hydrogen admixed in step d2) and d2’), respectively, is produced by water electrolysis using electrical power generated at least in part from non-fossil, renewable resources.11 . The process according any one of claims 7 to 10, wherein, in step d1 ) and dT), respectively, the high-boiling residues are converted into synthesis gas by a gasification process or a partial oxidation process.

12. The process according to claim 11 , wherein the thermal energy necessary for the gasification process or the partial oxidation process is provided at least in part by electrical power generated at least in part from non-fossil, renewable resources.

13. The process according to claim 11 or 12, wherein oxygen produced by water electrolysis is added in the gasification process or the partial oxidation process.

14. The process according to any one of claims 1 to 13, wherein, in step e), propene is converted into acetone by e1 ) alkylating benzene with propene to give cumene, and e2) oxidation of cumene via cumene hydroperoxide to give phenol and acetone.

15. The process according to any one of claims 1 to 13, wherein, in step e), propene is converted into acetone by e1 ’) hydrating propene to give isopropanol, and e2’) oxidation of isopropanol to give acetone.

16. The process according to claim 14 or 15, wherein oxygen produced by water electrolysis is used in oxidation step e2) and e2’), respectively.

17. The process according to claim 13 or 16, wherein the oxygen is produced by water electrolysis using electrical power generated at least in part from non-fossil, renewable resources.

18. The process according to any one of claims 1 to 17, wherein acetone condensates recycled in step c) are selected from the group consisting of mesityl oxide, diacetone alcohol, diacetoneamine, acetonin and phorone.

19. The process according to any one of claims 1 to 18, wherein step d) is: d) converting the high-boiling residues obtained in step b) into propene and further chemical material.

20. The process according to claim 19, wherein the process comprises the step: converting the further chemical material obtained by or obtainable by the process according to claim 19 to obtain a product PRF1.

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