Production of ethylene-derived chemicals with bio-based carbon content from pyrolysis oil

Abstract

A process for manufacturing one or more ethylene-derived chemicals having a bio-based carbon content, comprising the steps of: (a) providing a first ethylene stream by (a-i) providing a cracker feed stream comprising pyrolysis oil and fossil-based hydrocarbons, (a-ii) subjecting the cracker feed to steam cracking to obtain a cracker effluent, (a-iii) recovering the first ethylene stream from the cracker effluent; (b) providing a second ethylene stream having a bio-based carbon content; (c) combining the first ethylene stream and the second ethylene stream to obtain a combined ethylene stream; (d) converting the combined ethylene stream to at least one first generation ethylene-derived chemical selected from the group consisting of: (alpha) ethylene oxide, (beta) ethylbenzene, (gamma) ethylene dichloride; and (delta) propionaldehyde; and (e) optionally subjecting the first generation ethylene-derived chemical to a chemical conversion or a series of chemical conversions to obtain a downstream ethylene-derived chemical. The process allows for efficient operation of the steam cracker while allowing for the production of ethylene-derived chemicals having a predetermined bio-based carbon content.

Description

Chemicals derived from ethylene with bio-based carbon content produced from pyrolysis oil.

[0001] This invention relates to a method for manufacturing one or more ethylene-derived chemicals having a bio-based carbon content.

[0002] Chemical recycling aims to transform plastic waste into chemicals. It is a method in which the chemical structure of polymers is altered and converted into chemical building blocks, including monomers, which are then reused as feedstocks in chemical processes. Waste plastics can be converted into gaseous and liquid products through a pyrolysis process. These liquid products contain alkanes, isoalkanes, alkenes, cycloalkanes, and aromatic components. Therefore, the liquid products of the pyrolysis process (pyrolysis oil) can be used as feedstock for steam pyrolysis.

[0003] Ethylene is a key building block in the chemical industry. The primary pathway for ethylene production is based on the cracking of hydrocarbons, such as steam cracking. Important ethylene derivatives (at the ends of their respective chains) include (meth)acrylic acid, (meth)acrylates, isononol, ethylhexanol, and ethylene glycol. One of the challenges in manufacturing chemicals and intermediates from ethylene is that the starting materials are derived from fossil fuels, such as natural gas or crude oil, which are non-renewable resources.

[0004] In recent years, much work has been done to improve the sustainability of pyrolysis products. One approach is to partially replace fossil-based hydrocarbons such as naphtha with pyrolysis oil or bio-naphtha.

[0005] The use of co-feeds derived from pyrolysis oil obtained from the pyrolysis of recycled waste plastics is disclosed in WO 2022 / 067251 A1. The production of ethylene-derived products (such as alkylene oxides and alkanolamines) based on the pyrolysis of recycled waste is disclosed in WO 2021 / 092320 A1. The incorporation of renewable and / or recycled feedstocks into a mainstream of conventional feedstocks derived from petroleum, the conversion of such streams into ethylene, and the manufacture of specific dialkylphosphinates from this ethylene are disclosed in WO 2023 / 280613 A1 (Clariant). The production of bio-naphtha, and the steam cracking of hydrocarbons to obtain, in particular, ethylene and the production of ethylene derivatives, are disclosed, for example, in US 2012 / 0053379 A1 (Stora Enso).

[0006] Chemical recycling via pyrolysis and steam cracking of pyrolysis oil still faces several hurdles. First, steam crackers are highly capital-intensive and therefore require large-scale construction to benefit from economies of scale. This means ensuring large feed streams for the equipment. However, the supply of pyrolysis oil is limited and fluctuates in quantity. Therefore, large-volume substitution with fossil hydrocarbons such as naphtha remains challenging. Furthermore, undiluted pyrolysis oil may not meet steam cracker specifications. While pyrolysis can process any type of organic material, the presence of heteroatom-containing polymers (like PVC) in waste plastics can lead to contaminants (like organochlorides) in the pyrolysis oil. However, using fossil-based diluents or co-feeding with pyrolysis oil may easily render fossil resource conservation and greenhouse gas emission reductions negligible.

[0007] Over the past decade, demand for ethylene-derived chemicals with a certain bio-based carbon content has been increasing and is expected to increase further. One way to achieve this increased bio-based carbon content is to develop alternative synthetic pathways based on bio-feedback. This approach has certain drawbacks. In many cases, the synthetic pathways deviate significantly from established fossil-based manufacturing pathways. Therefore, existing production facilities become unusable, necessitating the construction of new facilities, which presents economic, environmental, and technological challenges. Furthermore, the current chemical industry, which uses naphtha and methane as its primary carbon sources, will have to shift to an economic model based on a variety of different feedstocks, increasing the complexity of chemical production.

[0008] As mentioned above, the technical possibilities for increasing the bio-based carbon content in pyrolysis products (ethylene) are limited. Therefore, there is a need for a method that allows for the efficient operation of steam pyrolysis plants while enabling the production of ethylene-derived chemicals with a predetermined bio-based carbon content.

[0009] This invention relates to a method for manufacturing one or more ethylene-derived chemicals having a bio-based carbon content, the method comprising the following steps:

[0010] (a) Providing the first ethylene flow via the following

[0011] (ai) provides a cracker feed stream containing pyrolysis oil and fossil-based hydrocarbons.

[0012] (a-ii) subject the pyrolyzer feed to steam pyrolysis to obtain the pyrolyzer effluent.

[0013] (a-iii) Recover the first ethylene stream from the effluent of the pyrolyzer;

[0014] (b) Providing a second ethylene stream with bio-based carbon content by subjecting the feedstock containing bioethanol to dehydration;

[0015] (c) Combine the first ethylene stream and the second ethylene stream to obtain a combined ethylene stream;

[0016] (d) Convert the combined ethylene stream into at least one first-generation ethylene-derived chemical selected from the following

[0017] (α) Ethylene oxide,

[0018] (β) Ethylbenzene,

[0019] (γ) dichloroethane; and

[0020] (δ)propionaldehyde; and

[0021] (e) Optionally, the first-generation ethylene-derived chemical may be subjected to a chemical transformation or a series of chemical transformations to obtain a downstream ethylene-derived chemical.

[0022] According to the present invention, a pyrolyzer-based ethylene stream (first ethylene stream) is combined with an ethylene stream having a known bio-based carbon content (second ethylene stream). By combining the ethylene streams, an ethylene stream with a defined bio-based carbon content is obtained, which can be adjusted by changing the blending ratio of the two ethylene streams, thereby enabling downstream production of ethylene-derived products with a predetermined bio-based carbon content. By using the second ethylene stream with a high bio-based carbon content, the combined ethylene stream has a defined minimum bio-based carbon content, and therefore a minimum bio-based carbon content in any downstream pyrolyzer-based ethylene derivatives can be ensured.

[0023] To more clearly define the terminology used herein, the following definitions are provided and, unless otherwise expressly stated, apply throughout this disclosure.

[0024] The terms "renewable" or "renewably sourced" are used synonymously with respect to chemical compounds and refer to chemical compounds containing a certain amount of renewable carbon, i.e., having reduced or no fossil-sourced carbon content. Renewable carbon involves all carbon sources that avoid or replace the use of any additional fossil carbon from the lithosphere. Renewable carbon can originate from the biosphere, atmosphere, or technosphere—but not from the lithosphere. Therefore, the expression "renewable" or "renewably sourced" specifically includes biomass-derived chemical compounds. It also includes compounds derived from waste (such as polymer residues) or waste streams derived from chemical production processes.

[0025] The term "bio-based" refers to organic carbon containing renewable sources, such as agricultural, plant, animal, fungal, microbial, marine, or forestry materials that exist in the natural environment in balance with the atmosphere.

[0026] The term "bio-based carbon content" refers to the amount of bio-based carbon in a material or product as a percentage of the total organic carbon (TOC).

[0027] The bio-based carbon content of a material can be measured using the ASTM D6866 method, which allows for the determination of the bio-based content using radioactive carbon analysis via accelerator mass spectrometry, liquid scintillation counting, and isotope mass spectrometry. When atmospheric nitrogen is bombarded by neutrons produced by ultraviolet radiation, it loses protons and forms carbon with a molecular weight of 14, which is radioactive. 14 C is immediately oxidized to carbon dioxide and represents a small but measurable portion of atmospheric carbon. Atmospheric carbon dioxide is cycled by green plants during photosynthesis to produce organic molecules. The cycle is complete when green plants or other life forms metabolize organic molecules to produce carbon dioxide, and the carbon dioxide is then able to return to the atmosphere. Therefore, carbon dioxide present in the atmosphere... 14 C becomes part of all life forms and their biological products.

[0028] The application of ASTM D6866 to derive "bio-based carbon content" is based on the same concept as radiocarbon dating, but does not use an age equation. This is achieved by deriving the radiocarbon content in an unknown sample. 14 The analysis is performed by comparing the amount of C) to the amount of radiocarbon in a current reference standard. This ratio is reported as a percentage, and the unit is "pMC" (percentage of modern carbon). If the material being analyzed is a mixture of present-day radiocarbon and fossil carbon (containing no radiocarbon), the obtained pMC value is directly related to the amount of bio-based material present in the sample. The current reference standard used for radiocarbon dating is the NIST (National Institute of Standards and Technology) standard, which is approximately equivalent to the known radiocarbon content in 1950 AD. 1950 AD was chosen because it represents the time before thermonuclear weapon tests that introduced large amounts of excess radiocarbon (known as "bomb carbon") into the atmosphere through each explosion. The 1950 reference value is expressed as 100 pMC. Before the peak of testing and the treaty that halted testing in 1963, "bomb carbon" in the atmosphere reached almost twice the normal level. Its distribution in the atmosphere has been approximated since its appearance, showing values ​​greater than 100 pMC for living plants and animals since 1950 AD. The distribution of bomb carbon has gradually decreased over time, and the current value is close to 107.5 pMC. Therefore, fresh biomass materials (such as corn) can produce radiocarbon signatures close to 107.5 pMC.

[0029] Petroleum-based carbon does not have the characteristic radiocarbon ratio of atmospheric carbon dioxide. Studies have noted that fossil fuels and petrochemical products have a radiocarbon ratio of less than about 1 pMC, and typically less than about 0.1 pMC, for example less than about 0.03 pMC. However, compounds derived entirely from renewable resources have at least about 95% modern carbon (pMC), and they can have at least about 99 pMC, including about 100 pMC.

[0030] Combining fossil carbon with contemporary carbon into a material results in a dilution of the contemporary pMC content. By assuming 107.5 pMC represents contemporary bio-based material and 0 pMC represents petroleum derivatives, the measured pMC value of the material will reflect the ratio of the two component types. Material 100% derived from contemporary biomass will give a radiocarbon signature close to 107.5 pMC. If the material is diluted with 50% petroleum derivatives, it will give a radiocarbon signature close to 54 pMC.

[0031] The bio-based content results are derived by defining 100% as equal to 107.5 pMC and 0% as equal to 0 pMC. In this respect, a sample measured at 99 pMC will give an equivalent bio-based content result of 93%.

[0032] The term "bioethanol" refers to ethanol obtained from biomass feedstocks, such as plant or non-crop feedstocks containing carbon sources that can be converted into ethanol, for example, through microbial metabolism.

[0033] "First-generation ethylene-derived chemicals" refers to the primary reaction products of ethylene, which can be chemically transformed or a series of chemical transformations to obtain downstream ethylene-derived chemicals.

[0034] The term "downstream ethylene-derived chemicals" refers collectively to any desired compound that appears in the value chain starting from first-generation ethylene-derived chemicals. Therefore, this expression includes both intermediates and final products. In some cases, a chemical compound can be both an intermediate and a final product simultaneously.

[0035] First ethylene flow

[0036] According to the method of the invention, a first ethylene stream is provided by subjecting the pyrolysis feed stream to steam cracking. The first ethylene stream is recovered from the pyrolysis effluent.

[0037] pyrolyzer feed stream

[0038] The pyrolysis feed stream contains pyrolysis oil and fossil-based hydrocarbons. In some embodiments, the pyrolysis feed stream also contains bio-naphtha.

[0039] In this embodiment, the pyrolyzer feed stream comprises, relative to the total weight of the pyrolyzer feed, the following:

[0040] 0.1 to 40 wt.% pyrolysis oil; and

[0041] 60 to 99.9 wt.% fossil-based hydrocarbons; preferably

[0042] 1 to 35 wt.% pyrolysis oil; and

[0043] 65 to 99 wt.% fossil-based hydrocarbons.

[0044] Fossil-based hydrocarbons used as cracker feedstocks are in particular ethane, propane, butane, and / or naphtha. Ethane, propane, and butane are components of natural gas and petroleum. Therefore, they can be obtained from natural gas processing or petroleum refining by separation from other hydrocarbons and subsequent refining, if necessary. Naphtha (fossil-based) can be derived from upstream refining processes such as atmospheric distillation columns, hydrocrackers, or coking units. Different types of fossil-based naphtha can be distinguished, for example, by their boiling points. Thus, "light naphtha" has a boiling point in the range of 30°C to 90°C and contains a major fraction of molecules with 5 to 6 carbon atoms, while "heavy naphtha" has a boiling point in the range of 90°C to 200°C and contains a major fraction of molecules with 6 to 12 carbon atoms. In the examples, the fossil-based naphtha is light naphtha.

[0045] The fossil-based hydrocarbon in the pyrolysis feed stream can be a mixture of two or more of ethane, propane, butane, or naphtha. It can also be substantially any one of ethane, propane, butane, or naphtha. Preferably, the fossil-based hydrocarbon is naphtha.

[0046] In one embodiment, the pyrolysis feed stream comprises 60 to 99.9 wt.% fossil-based hydrocarbons relative to the total weight of the pyrolysis feed. In another embodiment, the pyrolysis feed stream comprises 60 to 99.8 wt.% fossil-based hydrocarbons. In yet another embodiment, the pyrolysis feed stream comprises 55 to 99 wt.% fossil-based hydrocarbons.

[0047] pyrolysis oil

[0048] In the context of this invention, the term "pyrolysis" refers to the thermal decomposition or degradation of waste solid organic raw materials (such as plastics or rubber) under inert conditions, producing gaseous, liquid, and solid char portions. During pyrolysis, plastics and rubber are converted into a variety of chemicals, including gases such as H2, C1-C4 alkanes, C2-C4 olefins, acetylene, propyne, and 1-butyne, pyrolysis oils with boiling temperatures ranging from 25°C to 500°C, and char. The term "pyrolysis" includes slow pyrolysis, fast pyrolysis, flash catalytic pyrolysis, and catalytic pyrolysis. These types of pyrolysis differ in process temperature, heating rate, residence time, feed particle size, etc., resulting in different product qualities.

[0049] In the context of this invention, the term "pyrolysis oil" should be understood to mean any oil derived from the pyrolysis of waste solid organic raw materials, such as plastic waste or rubber waste.

[0050] In the context of this invention, the term "plastic waste" refers to any plastic material that is discarded after use, i.e., the plastic material has reached the end of its service life. Plastic waste can be pure polymer plastic waste, mixed plastic waste, or membrane waste, including filth, adhesive materials, fillers, residues, etc. Plastic waste has nitrogen content, sulfur content, halogen content, and optionally heavy metal content. Plastic waste can originate from any source containing plastic materials. Therefore, the term "plastic waste" includes industrial and household plastic waste, including used tires and agricultural and horticultural plastic materials. The term "plastic waste" also includes used petroleum-based hydrocarbon materials, such as used engine oil, machine oil, grease, wax, etc.

[0051] Typically, plastic waste is a mixture of different plastic materials, including hydrocarbon plastics such as polyolefins like polyethylene (HDPE, LDPE) and polypropylene, polystyrene and their copolymers, and polymers composed of carbon, hydrogen and other elements such as chlorine, fluorine, oxygen, nitrogen, sulfur, and silicon, such as chlorinated plastics like polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), nitrogen-containing plastics like polyamide (PA), polyurethane (PU), acrylonitrile butadiene styrene (ABS), oxygen-containing plastics like polyesters such as polyethylene terephthalate (PET), polycarbonate (PC), and silicone and / or rubbers such as sulfur-bridged crosslinked rubber. PET plastic waste is usually sorted out before pyrolysis because PET has a profitable resale value. Therefore, plastic waste to be pyrolyzed typically contains less than about 10% PET by weight based on the dry weight of the plastic material, preferably less than about 5% PET by weight, and most preferably substantially free of PET. One of the main components of waste from electrical and electronic equipment is polychlorinated biphenyls (PCBs). Typically, plastic materials contain additives such as processing aids, plasticizers, flame retardants, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, antioxidants, etc. These additives may contain elements other than carbon and hydrogen. For example, the presence of bromine is primarily associated with flame retardants. Heavy metal compounds can be used as light-resistant pigments and / or stabilizers in plastics; cadmium, zinc, and lead may be present in heat stabilizers and slip agents used in plastic manufacturing. Plastic waste may also contain residues. In the context of this invention, residues are contaminants that adhere to plastic waste. Additives and residues are generally present in amounts of less than 50% by weight of the total dry weight of the plastic, preferably less than 30% by weight, more preferably less than 20% by weight, and even more preferably less than 10% by weight.

[0052] Depending on the waste plastic material undergoing pyrolysis, crude pyrolysis oil can have varying levels of sulfur, nitrogen, halogens, and heavy metals (if present). If necessary, the pyrolysis oil can be purified before being used as the pyrolysis feed stream.

[0053] As used herein, the term “rubber material” is intended to refer to a polymeric material that constitutes an elastomer, a partially cross-linked (e.g., vulcanized) polymeric material that can be stretched to at least twice its original length at room temperature and, after being stretched and stress-relieved, springs back to approximately its original length within a short period of time.

[0054] Compared to thermoplastic materials (plastics), rubber materials exhibit improved thermal stability due to their partially cross-linked structure. Rubber does not melt, but it undergoes thermal degradation at higher temperatures, with the degradation temperature and rate depending particularly on the degree of cross-linking. Therefore, during pyrolysis, heat is not uniformly distributed within the rubber block, resulting in a significantly larger temperature gradient within the pyrolysis reactor. Systems for the pyrolysis of rubber materials should possess improved heat and mass transfer characteristics compared to systems used for the pyrolysis of plastics (thermoplastics).

[0055] Rubber materials that can be processed by pyrolysis can be of different types: waste rubber, such as natural or synthetic rubber containing polymers, such as polyisoprene, polychloroprene, polybutadiene, polyisobutylene, or copolymers, such as poly(styrene-butadiene-styrene). The term "rubber material" is intended to refer to natural rubber (1,4-polyisoprene) and synthetic rubber, such as styrene-butadiene rubber (SBR), butyl rubber (composed of polyisobutylene plus a diene, such as isoprene), or chloroprene (2-chloroprene-1,3-).

[0056] The rubber material to be pyrolyzed may further contain various additives, plasticizers, or fillers. An exemplary rubber material that can be pyrolyzed is a worn tire.

[0057] Useful pyrolysis oils can be characterized by their calorific value and / or bromine value. The calorific value can be evaluated according to DIN 51900. The olefin content can be determined with reference to the bromine value. "Bromine value" refers to the number of grams of bromine reacting with 100 g of material, ASTM method D1159.

[0058] In the embodiments, the pyrolysis oil exhibits at least one of the following parameters:

[0059] - Calorific value in the range of 35 to 46 kJ / g;

[0060] - Bromine value in the range of 2 to 160 g Br2 / 100g.

[0061] Typically, the pyrolysis feed stream contains 0.1 to 40 wt% pyrolysis oil relative to the total weight of the pyrolysis feed. In another embodiment, the pyrolysis feed stream contains 1 to 35 wt% pyrolysis oil.

[0062] In this invention, pyrolysis oil from waste solid organic feedstocks (including plastics and / or rubber) is recycled back as a starting material for high-value chemical products (including virgin plastics), thereby establishing a circular economy by combining different industrial methods. If the waste solid organic feedstocks have a bio-based carbon content greater than zero, the benefits accumulate. In this way, high-value chemical products with a steadily increasing bio-based carbon content can be obtained.

[0063] Therefore, in the embodiments, the pyrolysis oil is obtained from the pyrolysis of waste solid organic feedstock having a bio-based carbon content greater than zero, for example, having a bio-based carbon content of 1% or higher, or 3% or higher. Typically, the waste has a bio-based carbon content of 10% or less.

[0064] Bio-naphtha

[0065] Bio-naphtha can be produced from a complex mixture of fats and oils, such as vegetable oils, industrial greases, and waste oils. Therefore, bio-naphtha is a renewable energy source.

[0066] In one embodiment, bio-naphtha may be added to fossil naphtha to provide a first ethylene stream with a bio-based carbon content greater than zero.

[0067] In the embodiments, bio-naphtha is obtained at least in part by the hydrogenation of fatty acids, fatty acid derivatives, monoglycerides, diglycerides, or triglycerides, or combinations thereof. Bio-naphtha is known in itself, and its production is disclosed, for example, in US20120053379 A1. The starting material for the production of bio-naphtha may be based on tall oil. Tall oil is an oil product obtained from wood (such as pine and other coniferous trees). Typically, the starting material contains at least 75 wt.% tall oil fatty acids and no more than 25 wt.% tall oil resin acids. The starting material may contain other suitable vegetable oils, such as palm oil. The starting material is subjected to hydrodeoxygenation by methods known per se, such as those described, for example in US 20120053379 A1. The hydrodeoxygenation product is a mixture of hydrocarbons suitable for steam cracking.

[0068] In one embodiment, the pyrolyzer feed stream contains up to 10 wt.% bio-naphtha relative to the total weight of the pyrolyzer feed stream. In another embodiment, the pyrolyzer feed stream contains 0.1 to 10 wt.% bio-naphtha relative to the total weight of the pyrolyzer feed stream.

[0069] Steam cracking

[0070] Steam cracking is a petrochemical process in which saturated hydrocarbons with long molecular structures are broken down (i.e., cracked) into smaller saturated or unsaturated molecules. Typically, steam crackers are designed to produce light olefins, especially ethylene and propylene, as valuable byproducts.

[0071] Conventional steam cracking utilizes a pyrolysis furnace with two main sections: a convection section and a radiative section. The hydrocarbon feedstock typically enters the furnace as a liquid or, in the case of light feedstocks, as steam in the convection section, where it is typically heated and, if necessary, vaporized through indirect contact with hot exhaust gases from the radiative section and through direct contact with steam. The vaporized feedstock and steam mixture is then introduced into the radiative section where cracking occurs.

[0072] The resulting stream, typically at temperatures in the range of 500°C to 650°C, enters a combustion-type tubular reactor and is heated to temperatures typically in the range of 750°C to 875°C for 0.1 to 0.5 s, with residence time, temperature profile, and partial pressure controlled. During this short reaction time, the hydrocarbons in the feedstock are broken down into smaller molecules, producing light olefins such as ethylene, propylene, butene, other small-molecule olefins, and dienes as the main products, excluding methane. These reaction products are suitably and typically exit the radiant tube at temperatures in the range of 800°C to 850°C, and preferably cooled to temperatures typically in the range of 550°C to 650°C within 0.02 to 0.1 s to prevent degradation of highly reactive compounds through secondary reactions. The resulting reaction products then exit the furnace for further downstream processing.

[0073] Processing of pyrolysis gas

[0074] In this article, the indicator "C" x "C" refers to a hydrocarbon containing x carbon atoms. x+ "C" refers to a hydrocarbon or mixture of hydrocarbons containing x or more carbon atoms, and "C" x- "Refers to hydrocarbons or mixtures of hydrocarbons containing x or fewer carbon atoms."

[0075] Typically, cracker effluent mixtures containing light olefins such as ethylene, propylene, butene, other small molecule olefins, and dienes, in addition to methane, are separated using a series of separation and chemical treatment steps. This process typically also produces light byproducts such as hydrogen, carbon oxides, light saturated hydrocarbons, and water.

[0076] The hot pyrolysis gas leaving the pyrolysis unit is rapidly cooled to prevent unwanted subsequent reactions. This is typically done in several steps. In the first step, the pyrolysis gas is cooled to approximately 450°C via a heat exchanger. Further cooling occurs via direct contact between the pyrolysis gas and a high-boiling-point liquid (often called quench oil). Quenching causes partial condensation of the pyrolysis gas. In this step, the C-rich gas is cooled... 10+ The heavy stream of hydrocarbons is separated from the cracked gas. Further cooling of the cracked gas takes place in a water quench tower used for primary fractionation, cooling the gas to approximately 30°C. In this step, C... 5-9 Fraction (commonly known as pyrolysis gasoline) and C 4- Component separation.

[0077] The recovery of various olefin products from cracked gases is typically achieved through fractionation using a series of distillation steps or columns to separate the various components. The unit that separates hydrocarbons with one carbon atom (C1) from the lighter fraction is called a "demethanizer." The unit that separates hydrocarbons with two carbon atoms (C2) from the heavier fraction is called a "deethaner." The unit that separates hydrocarbon fractions with three carbon atoms (C3) from the heavier fraction is called a "depropanizer." The unit that separates hydrocarbon fractions with four carbon atoms (C4) from the heavier fraction is called a "debutanizer."

[0078] It has a high carbon number fraction (C 5+ The remaining heavier components can be used as gasoline or recycled back to the cracker.

[0079] Various fractionation units can be arranged in various sequences to provide desired results based on various feedstocks. For this purpose, the sequence in which the demethanizer is used first is often referred to as the "front-end demethanizer" sequence. Similarly, when the deethaner is used first, it is often referred to as the "front-end deethaner" sequence. And, when the depropanizer is used first, it is often referred to as the "front-end depropanizer" sequence.

[0080] In a conventional front-end demethanizer sequence, hydrocarbons (C1 to C2) with one to five or more carbon atoms per molecule are present. 5+ The cracked gas first enters a demethanizer, where methane and the lighter fraction (hydrogen) are separated as overhead distillate. The demethanizer operates at relatively low temperatures, typically ranging from about -100°C to about 25°C.

[0081] The heavy fraction leaving the demethanizer mainly consists of C2 to C3. 5+ Molecular composition. These heavy fractions are then routed to a deethanizer, where C2 hydrocarbons are collected at the top, and C3 to C4 hydrocarbons are collected from the top. 5+The compound exits as the bottom distillate. The C2 fraction exiting the top of the deethanizer can be fed to an acetylene converter or acetylene removal unit. Since some methane remains dissolved in the heavy fraction exiting the demethanizer and ultimately in the C2 fraction exiting the deethanizer, the C2 fraction stream can then be sent to a demethanizer to remove the remaining methane.

[0082] The C2 fraction, from which methane has been removed, is then fed to a C2 separator, which produces ethylene as a light product and ethane as a heavy product. The C3 fraction from the bottom of the deethanizer is then transferred to the C2 separator. 5+ The stream is fed along the route to a propane stripper, which sends the C3 component to the top of the column and transfers the C4 to C5 components. 5+ The components are sent down.

[0083] Before being fed into the C3 separator, the C3 product can be hydrogenated to remove C3 acetylene and diene, in which the product is separated into propylene at the top and propane at the bottom.

[0084] From C4 to C 5+ The feed is fed to a butanizer, which produces a C4 component at the top, with the remaining C4 being... 5+ The components exit as bottom distillate. The C4 stream and C... 5+ Both streams are hydrogenated separately to remove unwanted acetylene and diene.

[0085] In a typical front-end deethaner sequence, C1 to C2 are present. 5+ The cracked gas from the components first enters the deethanizer. The light fraction leaving the deethanizer consists of C2 and C1 components, as well as any hydrogen gas (C2). 2- (Fractions). These light fractions are fed into a demethanizer (C). 2- A demethanizer is used, in which hydrogen and C1 are removed as light tail fractions and C2 components are removed as heavy tail fractions. The C2 stream exiting the bottom of the demethanizer can be fed to an acetylene converter and then to a C2 separator, which produces ethylene as a light product and ethane as a heavy product. The heavy fraction exiting the demethanizer (which consists of C3 to C4 components) is then removed. 5+ The components are fed along a route to a depropanizer, which sends the C3 component to the top of the column and transfers the C4 component to the C5 component. 5+ The components are fed downwards. The C3 product is fed into a C3 separator, where it is separated into propylene at the top and propane at the bottom, while the C4 to C5 products are separated. 5+ The feed is fed to a butanizer, which produces C4 compounds at the top. The remainder leaves as bottom distillate for use in gasoline or is recycled back to the cracking process as feed. Similar to the front-end demethanizer sequence, C3, C4, and C4 compounds can be processed. 5+The stream is hydrogenated separately to remove unwanted acetylene and diene.

[0086] In a typical front-end propane dehydrogenator sequence, hydrocarbons with one to five or more carbon atoms per molecule (C1 to C4) are present. 5+ The quenched and acid-free gas first enters the depropanizer. The heavy fraction leaving the depropanizer is from C4 to C6. 5+ Component composition. These are fed to a butanizer, where the C4 component and lighter compounds are collected at the top, with the remainder of the feed exiting as bottoms distillate, which can be used for gasoline or other chemical recovery. These streams can be hydrotreated separately to remove unwanted acetylene and dienes. The top fraction of the propaneizer (containing C1 to C3 components) can be fed to an acetylene converter and then to a demethanizer system, where the C1 component and any remaining hydrogen are removed as tops distillate. The heavy fraction (containing C2 and C3 components) leaving the demethanizer system is introduced into a deethanizer, where the C2 component is removed from the top and the C3 compounds are collected from the bottom. The C2 component is then fed to a C2 separator, which produces ethylene as a light product and ethane as a heavy product. The C3 stream is fed into a C3 separator, which separates the C3 material, sending propylene to the top and propane to the bottom.

[0087] Similar to the front-end demethanizer sequence, saturated C2 hydrocarbons and / or saturated C3 hydrocarbons or a portion thereof obtained from the front-end deethaner or front-end depropanizer sequence can be recycled back into the cracking process as feed.

[0088] Ethylene recovered from the pyrolysis effluent in this manner is provided as a first ethylene stream. In an embodiment, the first ethylene stream is provided at a flow rate (first flow rate) in the range of 10 t / h to 1000 t / h.

[0089] Second ethylene stream

[0090] The second ethylene stream is obtained by dehydrating ethanol from a renewable source (i.e., bioethanol).

[0091] Production of bioethanol

[0092] In this invention, bioethanol refers to ethanol obtained from biomass feedstocks (such as plant or non-crop feedstocks containing carbon sources that can be converted into ethanol, for example, through microbial metabolism). Typical examples of carbon sources are starch, sugars like pentoses or hexoses such as glucose, fructose, sucrose, xylose, arabinose, or plant degradation products, hydrolysates of cellulose, or juices of sugarcane, sugar beets, etc., containing large amounts of the above components.

[0093] Biomass feedstocks can come from several sources. Bioethanol production can be based on food crop feedstocks such as corn and sugarcane, bagasse, and cassava (a first-generation bio-feedstock).

[0094] Another source of biomass feedstock is lignocellulosic material from agricultural crops (second-generation biomass feedstock). Potential feedstocks include agricultural residue byproducts such as rice, straw (e.g., wheat, oat, and barley straw), rice husks, and corn stalks. Biomass feedstock can also be waste from the forestry industry (wood waste) and sawdust, or waste specifically produced as ethanol crops. Switchgrass and elephant grass can be used as dedicated crops for ethanol conversion.

[0095] First-generation bioethanol is produced through four basic steps:

[0096] (1) Amylase-mediated saccharification or hydrolysis into sugar

[0097] (2) Microbial fermentation of sugar

[0098] (3) Purify by distillation to obtain aqueous ethanol

[0099] (4) Dehydration (water removal) to produce anhydrous ethanol

[0100] Second-generation feedstocks are considered renewable and sustainable carbon sources. Pretreatment of these feedstocks is a fundamental prerequisite before they undergo enzymatic hydrolysis, fermentation, distillation, and dehydration. Pretreatment involves milling and exposure to acid and heat to reduce the size of plant fibers and hydrolyze a portion of the material to produce fermentable sugars. Saccharification uses enzymes to hydrolyze another portion into sugars. Finally, various sugars (pentoses and hexoses) are converted into ethanol through fermentation by bioengineered microorganisms. Bioethanol production is well-known and carried out on a large industrial scale.

[0101] Renewable sources of ethanol can also be obtained from carbonaceous waste, such as waste from the chemical industry, garbage, and sewage sludge. Ethanol production from waste can be accomplished by gasifying it into syngas and then catalytically converting it into ethanol; see, for example, *Recent Advances in Thermo-Chemical Conversion of Biomass*, 2015, pp. 213-250, https: / / doi.org / 10.1016 / B978-0-444-63289-0.00008-9 and *Nature Communications*, 11, 827 (2020), https: / / doi.org / 10.1038 / s41467-020-14672-8.

[0102] Dehydration of renewable ethanol sources

[0103] The catalytic dehydration of ethanol to produce ethylene is a well-known method. This reaction is typically carried out at 300°C to 400°C and under moderate pressure in the presence of a catalyst. Catalysis is reviewed in *Ind & Eng Chem Research*, 52, 28, 9505-9514 (2013), *Materials*, 6, 101-115 (2013), and *ACS Omega*, 2, 4287-4296 (2017). Examples of catalysts include activated alumina or silica, phosphoric acid impregnated on coke, heteropolyacids (HPA salts), silica-alumina, molecular sieves such as ZSM-5 or SAPO-11 zeolites, other zeolites, or modified zeolites of various molecular structures, with zeolites and HPA salts being preferred.

[0104] Ethanol dehydration is described, for example, in WO 2009 / 098268, WO 2010 / 066830, WO 2009 / 070858 and the prior art discussed therein, WO 2011 / 085223 and the prior art discussed therein, US 4,234,752, US 4,396,789, US 4,529,827 and WO 2004 / 078336.

[0105] Ethanol dehydration reactions are typically carried out in the gas phase in contact with a heterogeneous catalyst bed using fixed-bed or fluidized-bed reactors. For fixed-bed reactors, operation can be isothermal (with an external heating system) or adiabatic (in the presence of a heat transfer fluid). The feedstock is vaporized and heated to the desired reaction temperature; as the reaction proceeds in the reactor, the temperature decreases. Multiple reactor beds are often used in series to maintain the temperature decrease in each bed within a controllable range. The cooled effluent from each bed is further heated to reach the desired inlet temperature for the subsequent beds. Additionally, a portion of the water is recycled along with the fresh, unreacted ethanol. The presence of water helps to mitigate the temperature decrease in each bed.

[0106] Prior to dehydration, the renewable ethanol feedstock can be sent to a pretreatment section to remove mineral contaminants, which would otherwise be detrimental to downstream catalytic reactions. Pretreatment may involve contacting the renewable ethanol feedstock with cation and / or anion exchange resins. After a period of operation, the resins can be regenerated to restore their ion exchange capacity by passing a regenerant solution through one or more resin beds. The two sets of beds are preferably operated in parallel to maintain continuous operation. One set of resin beds is appropriately regenerated while the other set is used for pretreatment.

[0107] In isothermal designs, the catalyst is placed inside the tubes of a vertically arranged, shell-and-tube fixed-bed reactor (shell-and-tube design). The heat transfer medium (such as molten salt or oil) circulates within the shell to provide the required heat. Baffles can be placed on the shell side to facilitate heat transfer. The cooled heating medium is externally heated and recirculated. Compared to adiabatic reactors, the temperature drop on the process side can be reduced. Better temperature control leads to increased selectivity for ethylene formation and a reduction in the amount of undesirable byproducts. The temperature is maintained at a roughly constant level in the range of 300°C to 350°C. Ethanol conversion is between 98% and 99%, and the selectivity for ethylene is between 94 and 97 mol%. Due to the rate of coke deposition, the catalyst must be regenerated frequently. Depending on the type of catalyst used, the cycle life is between 3 weeks and 4 months, followed by regeneration, for example, every 3 days.

[0108] In adiabatic designs, the endothermic reaction is supplied by a preheated inert diluent, such as steam. Typically, three fixed-bed reactors can be used, with an intermediate furnace used to reheat the ethanol / steam mixed feed stream to each reactor. Feeding ethanol with steam results in less coke formation, longer catalyst activity, and higher yields.

[0109] Another approach is the fluidized bed method. Fluidized bed systems offer excellent temperature control within the reactor, thereby minimizing byproduct formation. The heat distribution rate in fluidized bed operation approaches isothermal conditions. The endothermic reaction is supplied by a hot-recycled silica-alumina catalyst returned from the catalyst regenerator. Therefore, external heating of the reactor is not required.

[0110] After dehydration, the reaction mixture undergoes a separation step. Typical separation schemes involve rapid cooling of the reaction gases, for example in a water quencher, which separates most of the byproduct water and unreacted ethanol from ethylene and other light components, which exit, for example, from the top of the quencher. In one type of separation scheme, the water-washed ethylene stream is immediately subjected to alkaline washing (e.g., in a column) to remove trace amounts of CO2. The gaseous stream may proceed directly to a compressor or first through a buffer gas holder and then to a gas compressor. After compression, the gas is cooled by refrigeration and then passed through an adsorber with, for example, activated carbon to remove trace amounts of heavy components (e.g., C4) (if present). Following the adsorber, after the ethylene product leaves the unit, there is a desiccant drying and dust filtration step. This separation scheme produces ethylene with a purity of 99%+. If desired, the ethylene is further purified by alkaline washing and desiccant drying, and fractionated in a cryogenic column to obtain the final product.

[0111] Several commercial methods developed jointly by Braskem, Chematur, British Petroleum (BP), and Axens with Total and the French Institute of Petroleum Renewable Energy (IFPEN) are currently in operation. These methods differ in, for example, their process conditions, catalysts, and the thermal integration schemes employed. BP's (now Technip) method is called Hummingbird. In this process, heteropolyacids are used as catalysts, and the reactors operate at 160°C to 270°C and 1 to 45 bar. Unreacted ethanol is recycled back to the reactors. The method developed by Axens is called Atol. It uses two fixed-bed adiabatic reactors operating at 400°C to 500°C. Chematur's process operates with four adiabatic tubular reactors. This process employs a Syndol catalyst (primarily Al₂O₃-MgO / SiO₂), developed by American Halcon Scientific Design, Inc. in the 1980s. In the Blasco method, the adiabatic reactor feed is largely diluted with steam. In this method, the reactor operates at 180°C to 600°C, preferably 300°C to 500°C, and at 1.9 to 19.6 bar. Alumina or silica-alumina catalysts are used. The Blasco method is described in more detail in US 4,232,179. Process control according to the Blasco method is particularly preferred.

[0112] In an embodiment, a second ethylene flow is provided at a flow rate (second flow rate) in the range of 10 t / h to 1000 t / h.

[0113] Blending of the first ethylene stream and the second ethylene stream

[0114] The first and second ethylene streams are mixed at a ratio as desired for the bio-based carbon content in the ethylene-derived chemicals. The bio-based carbon content in the ethylene-derived chemicals can be calculated using the following equation:

[0115]

[0116] in

[0117] A: The ratio between the second ethylene stream and the first ethylene stream

[0118] B1: Bio-based carbon content of the first ethylene stream

[0119] B2: Bio-based carbon content of the second ethylene stream

[0120] C: The ratio of the number of carbon atoms derived from ethylene to the total number of carbon atoms in the molecules of ethylene-derived chemicals.

[0121] Q: Bio-based carbon content in ethylene-derived chemicals.

[0122] In an embodiment, the ratio of the first ethylene flow to the second ethylene flow is adjusted, for example, by adjusting the ratio of the flow rate of the second ethylene flow (second flow rate) to the flow rate of the first ethylene flow (first flow rate), such that Q is 3% or higher. In an embodiment, Q is 5% or higher, particularly 10% or higher.

[0123] Chemical transformation of the combined ethylene stream

[0124] According to the present invention, the combined ethylene stream is converted into at least one first-generation ethylene-derived chemical selected from the following.

[0125] (α) Ethylene oxide,

[0126] (β) Ethylbenzene,

[0127] (γ) dichloroethane; and

[0128] (δ)propionaldehyde.

[0129] Optionally, the first-generation ethylene-derived chemicals may be subjected to chemical transformation or a series of chemical transformations to obtain downstream ethylene-derived chemicals.

[0130] First-generation ethylene-derived chemicals and downstream ethylene-derived chemicals have limited bio-based carbon content.

[0131] Chemical transformations, or a series of chemical transformations, may include reactions with carbon-containing reagents, resulting in the carbon atoms in the molecules constituting the first-generation ethylene-derived chemicals and / or downstream ethylene-derived chemicals being of mixed origin. In a preferred embodiment, the ratio of the number of carbon atoms from the combined ethylene stream to the total number of carbon atoms in the molecule of the first-generation ethylene-derived chemicals and / or downstream ethylene-derived chemicals is ≥ 0.25.

[0132] Ethylene oxide

[0133] In the embodiments, the first-generation ethylene-derived chemical is ethylene oxide. Therefore, in one embodiment, step d) includes the epoxidation reaction of the combined ethylene streams to produce ethylene oxide with a bio-based carbon content.

[0134] Ethylene oxide is produced in large quantities and is primarily used as an intermediate in the production of several industrial chemicals. Suitable epoxidation catalysts are typically obtained by depositing metallic silver onto a support. Highly selective silver-based epoxidation catalysts have been developed, which, in addition to silver as the active component, contain promoters to improve the catalytic properties of the catalyst, as described, for example, in WO 2007 / 122090 A2 and WO 2010 / 123856 A1. Examples of promoters include alkali metal compounds and / or alkaline earth metal compounds, as well as transition metals such as rhenium, tungsten, or molybdenum.

[0135] Suitable catalysts typically contain 20% to 35% or 25 to 45 wt.% silver relative to the weight of the catalyst.

[0136] Various porous refractory materials can be used as the carrier material, such as activated carbon, titanium dioxide, zirconium oxide, silicon dioxide, alumina, or ceramic compositions or mixtures of these materials. Preferably, the refractory carrier is an alumina carrier. The carrier preferably has a thickness of 0.5 to 3.0 m. 2 / g of BET surface area.

[0137] Suitable catalysts can be obtained through the following methods

[0138] i) Impregnating the refractory carrier with a silver impregnation solution, preferably under reduced pressure; and optionally subjecting the impregnated refractory carrier to drying; and

[0139] ii) subjecting the impregnated refractory carrier to a calcination process;

[0140] Steps i) and ii) can be repeated optionally.

[0141] The epoxidation of ethylene preferably involves reacting ethylene and oxygen in the presence of an epoxidation catalyst as described above. Epoxidation can be carried out by any method known to those skilled in the art. All reactors that are available in existing ethylene oxide production methods can be used; for example, externally cooled shell-and-tube reactors (see Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A-10, pp. 117-135, 123-125, VCH-Verlagsgesellschaft, Weinheim, 1987) or reactors with a loose catalyst bed and cooling tubes, such as those described in DE 34 14 717 A1, EP 0082 609 A1 and EP 0 339 748 A2.

[0142] Epoxidation is preferably carried out in at least one tubular reactor, and more preferably in a shell-and-tube reactor. On a commercial scale, ethylene epoxidation is preferably carried out in a multi-tube reactor containing thousands of tubes. The catalyst is packed into the tubes, which are then placed in a shell filled with coolant. In commercial applications, the inner tube diameter is typically in the range of 20 to 40 mm (see, for example, US 4,921,681 A) or greater than 40 mm (see, for example, WO 2006 / 102189 A1).

[0143] To prepare ethylene oxide from ethylene and oxygen, the reaction can be carried out under conventional reaction conditions as described, for example, in DE 25 21 906 A, EP 0 014 457 A2, DE 23 00 512 A1, EP 0 172 565 A2, DE 24 54 972 A1, EP 0 357 293 A1, EP 0 266015 A1, EP 0 085 237 A1, EP 0 082 609 A1, and EP 0 339 748 A2. An inert gas, such as nitrogen, or a gas inert under the reaction conditions (e.g., vapor, methane), along with optional reaction moderators (e.g., halogenated hydrocarbons such as chloroethane, vinyl chloride, or 1,2-dichloroethane), can be additionally mixed into the reaction gas containing ethylene and molecular oxygen.

[0144] The reactant gas preferably contains, by weight, 0 to 15 ppm, preferably 0.1 to 8 ppm, a chlorinated reaction modifier, such as chloroethane, vinyl chloride, or 1,2-dichloroethane, based on the total weight of the reactant gas. The remainder of the reactant gas typically includes hydrocarbons such as methane and inert gases such as nitrogen. Additionally, the reactant gas may contain other materials such as vapor, carbon dioxide, or rare gases.

[0145] The concentration of carbon dioxide in the feed (i.e., the gas mixture fed into the reactor) typically depends on the catalyst selectivity and the efficiency of the carbon dioxide removal equipment. The carbon dioxide concentration in the feed is preferably at most 3 vol.-%, more preferably less than 2 vol.-%, and most preferably less than 1 vol.-%, relative to the total volume of the feed. Examples of carbon dioxide removal equipment are provided in US 6,452,027 B1.

[0146] The epoxidation of ethylene to ethylene oxide is typically carried out at elevated catalyst temperatures. The catalyst temperature is preferably in the range of 150°C to 350°C, more preferably 180°C to 300°C, particularly preferably 190°C to 280°C, and especially preferably 200°C to 280°C.

[0147] Epoxidation is preferably carried out at a pressure in the range of 5 to 30 bar. Unless otherwise stated, all pressures herein are absolute pressures. Epoxidation is more preferably carried out at a pressure in the range of 5 to 25 bar, such as 10 to 24 bar, and particularly 14 to 23 bar.

[0148] The epoxidation of ethylene is preferably carried out under conditions conducive to obtaining a reaction mixture containing at least 2.3 vol.% ethylene oxide. In other words, the ethylene oxide outlet concentration (ethylene oxide concentration at the reactor outlet) is preferably at least 2.3 vol.%. More preferably, the ethylene oxide outlet concentration is in the range of 2.5 to 4.0 vol.%, and most preferably, in the range of 2.7 to 3.5 vol.%.

[0149] Epoxidation is preferably carried out continuously. The epoxidation of ethylene can advantageously be carried out in a recycling process. After each pass, newly formed ethylene oxide and byproducts formed in the reaction are removed from the product gas stream. The remaining gas stream is replenished with the required amounts of ethylene, oxygen, and a reaction moderator and reintroduced into the reactor. Separation of ethylene oxide from the product gas stream and its subsequent treatment can be carried out using conventional methods of the prior art (see Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A-10, pp. 117-135, 123-125, VCH-Verlagsgesellschaft, Weinheim, 1987).

[0150] The epoxidation of ethylene proceeds with less than 100% selectivity and is accompanied by the generation of carbon dioxide. It should be understood that because the starting ethylene is carbon neutral, the emission of carbon dioxide byproducts does not affect the carbon footprint of this method.

[0151] Hydrolysis of ethylene oxide

[0152] In the embodiments, the downstream ethylene-derived chemicals are selected from ethylene glycol, polyethylene glycol, and ethylene glycol ethers.

[0153] In one embodiment, step e) includes the hydrolysis of ethylene oxide to produce ethylene glycol and / or ethylene glycol ethers. Ethylene glycol and ethylene glycol ethers can be used in a wide variety of industrial applications, such as in the fields of food, beverages, tobacco, cosmetics, thermoplastic polymers, curable resin systems, detergents, and heat transfer systems.

[0154] The hydrolysis of ethylene oxide is known and typically involves reacting ethylene oxide with water, appropriately using an acidic or basic catalyst. For example, to obtain primarily ethylene glycol (1,2-ethylene glycol) and a smaller amount of ethylene glycol ether, ethylene oxide can be reacted with ten molar excess water in the liquid phase in the presence of an acid catalyst (e.g., 0.5 to 1.0 wt.-% sulfuric acid based on the total reaction mixture) at 50°C to 70°C and 1 bar absolute pressure, or in the gas phase at 130°C to 240°C and 20 to 40 bar absolute pressure, preferably in the absence of a catalyst.

[0155] If the proportion of water decreases, the proportion of ethylene glycol ethers in the reaction mixture increases. The resulting ethylene glycol ethers can be diethers, triethers, tetraethers, or higher ethers. Alternative ethylene glycol ethers can be prepared by converting ethylene oxide with an alcohol (especially a primary alcohol, such as methanol or ethanol), replacing at least a portion of the water with the alcohol. Higher ethylene glycol ethers (polyethylene glycol) are prepared by anionic polymerization of ethylene oxide. For molar masses up to about 40,000 g / mol, bases such as sodium ethoxide or potassium tert-butoxide are used for initiation. Polyethylene glycols with molar masses up to 3,000,000 g / mol are obtained using basic catalysts such as alkaline earth metal oxides or carbonates.

[0156] Amination reaction of ethylene oxide

[0157] In another embodiment, step e) includes the amination reaction of ethylene oxide to produce ethanolamine and / or ethyleneamine as downstream ethylene-derived chemicals. Ethanolamine can be used, for example, in the treatment of natural gas (“desulfurization”). Ethyleneamine is used as a solvent, stabilizer, and starting material for the synthesis of chelating agents, fungicides, micronutrients, synthetic resins, fibers, pharmaceuticals, inhibitors, and surfactants.

[0158] The amination of ethylene oxide in the first step provides ethanolamines, such as monoethanolamine and diethanolamine, which can be amination in subsequent steps to give the desired ethyleneamine. These reactions occur under high pressure and high temperature and also lead to the formation of many byproducts.

[0159] To obtain ethanolamines, the amination reaction typically involves reacting ethylene oxide with ammonia, an alkylamine (such as monoalkylamines and dialkylamines), an alkanolamine, or an aromatic amine, preferably ammonia. Anhydrous ammonia or aqueous ammonia solution can be used, but anhydrous ammonia is typically used to facilitate the production of monoethanolamines. For methods suitable for converting ethylene oxide to ethanolamines, see, for example, US 4,845,296. The ethanolamine obtained is preferably monoethanolamine, diethanolamine, or a mixture of both. Most preferably, the ethanolamine is monoethanolamine.

[0160] The amination of ethylene oxide with ammonia produces a stream containing ammonia, monoethanolamine, diethanolamine, and triethanolamine. The ethanolamine can be separated from this stream. Alternatively, the stream can be at least partially fed into a subsequent amination reaction with, for example, ammonia to obtain ethylenediamines, such as ethylenediamine.

[0161] Suitable catalysts may contain catalytically active compounds on a solid support. Typically, catalysts contain at least one metal selected from the group consisting of: nickel, chromium, cobalt, copper, ruthenium, iron, calcium, magnesium, strontium, lithium, sodium, potassium, barium, cesium, tungsten, silver, zinc, uranium, titanium, rhodium, palladium, platinum, iridium, osmium, gold, molybdenum, rhenium, cadmium, lead, rubidium, boron, and manganese, or mixtures thereof.

[0162] The temperature used during amination is typically between 120°C and 300°C, preferably between 175°C and 225°C. The pressure used during amination is typically between 8 and 40 MPa, preferably between 15 and 30 MPa.

[0163] Alkylation of benzene and ethylene

[0164] In another embodiment, the first-generation ethylene-derived chemical is ethylbenzene. Therefore, in an embodiment, step d) of the invention comprises reacting the combined ethylene stream with benzene in an alkylation reaction to produce ethylbenzene.

[0165] Benzene can be alkylated with ethane, preferably in the liquid phase, to produce ethylbenzene. Typically, alkylation is carried out at temperatures between 80°C and 130°C in the presence of a Lewis acid catalyst (such as AlCl3, AlBr3, FeCl3, ZrCl4, and BF3, with AlCl3 being preferred). Chloroethane or hydrogen chloride can be used as a catalyst promoter. Further details can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A10, pp. 35-40, 1987.

[0166] Ethylbenzene dehydrogenation yields styrene and polymers

[0167] In another embodiment, ethylbenzene is subjected to a dehydrogenation reaction to produce styrene as a downstream ethylene-derived chemical. To produce styrene, the obtained ethylbenzene is dehydrogenated in the vapor phase over a catalyst containing iron oxide. The dehydrogenation can be carried out adiabatically or isothermally. Further details can be found in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, Vol. 34, pp. 386-390, 2003.

[0168] The obtained styrene can be polymerized in a conventional manner into polystyrene or polystyrene copolymers, such as styrene-butadiene copolymers.

[0169] Dichloroethane, vinyl chloride, and polymers

[0170] In another embodiment, step d) includes converting the combined ethylene stream into dichloroethylene (1,2-dichloroethane) as a first-generation ethylene-derived chemical. The production of 1,2-dichloroethane is primarily achieved via a ferric chloride (III) catalytic reaction of ethylene and chlorine. It is also produced via oxychlorination of ethylene catalyzed by copper chloride (II).

[0171] Known methods for the oxychlorination of ethylene to produce 1,2-dichloroethane involve the reaction of ethylene, hydrogen chloride, and a mixture of oxygen or an oxygen-containing gas (e.g., air) in the gas phase on a fixed or fluidized catalyst bed. These conditions are generally described in U.S. Patent Nos. 3,488,398. Typical catalysts used in oxychlorination reactions comprise copper compounds, preferably copper chloride, as the active catalytic component, uniformly deposited on fine particles of a support or fluidizable support. The support is preferably alumina.

[0172] 1,2-Dichloroethane is primarily used to industrially produce vinyl chloride via thermal cracking, in the presence of dehydrochlorination. For details of the cracking process, refer to Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, Vol. 8, pp. 59-62. Industrially, vinyl chloride is primarily used only for industrial polymerization to poly(vinyl chloride). Various polymerization methods for obtaining poly(vinyl chloride) are known. For details of the polymerization methods, refer to Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, Vol. 29, pp. 1-29.

[0173] Hydroformylation of ethylene

[0174] In another embodiment, step d) includes converting the combined ethylene stream into propionaldehyde as a first-generation ethylene-derived chemical. In one embodiment, the ethylene is subjected to hydroformylation to produce propionaldehyde.

[0175] Hydroformylation, or oxidation, is an important large-scale industrial method for the preparation of aldehydes from olefins, carbon monoxide, and hydrogen. These aldehydes can optionally be hydrogenated with hydrogen in the same operation or subsequently in a separate hydrogenation step to produce the corresponding alcohol. Typically, hydroformylation is carried out in the presence of a catalyst homogeneously dissolved in the reaction medium. The catalyst used is usually a carbonyl complex of a transition metal (especially Co, Rh, Ir, Pd, Pt, or Ru), which can be unmodified or modified with ligands containing, for example, amines or phosphine. A summary description of the methods used in large-scale industrial practice can be found in J. Falbe, “New Syntheses with Carbon Monoxide”, Springer Verlag, 1980, pp. 162 and onwards, US 3,527,809; 3,917,661; 4,148,830; 4,742,178; 4,769,984; 4,885,401; 6,049,011.

[0176] Ethylene is preferably hydroformylated using a ligand-modified rhodium carbonyl catalyst. The hydroformylation of ethylene can be carried out at temperatures ranging from 50°C to 200°C, preferably from 60°C to 150°C, and more preferably from 70°C to 120°C.

[0177] In one embodiment, the hydroformylation reaction is carried out at low pressure, for example in the range of 0.05 to 50 MPa (absolute value), and preferably in the range of about 0.1 MPa to 30 MPa, most preferably at a pressure below 5 MPa. Desiredly, the partial pressure of carbon monoxide is not greater than 50% of the total pressure.

[0178] The ratio of carbon monoxide, hydrogen, and ethylene in the hydroformylation reaction medium can be selected within a wide range. In some embodiments, based on the total amount of CO, hydrogen, and ethylene, CO is about 1 to 50 mol-%, preferably about 1 to 35 mol-%; H2 is about 1 mol-% to 98 mol-%, preferably about 10 mol-% to 90 mol-%; and ethylene is about 0.1 to 35 mol-%, preferably about 1 to 35 mol-%.

[0179] Hydroformylation reactions are preferably carried out in the presence of both liquid and gas phases. The reactants are typically in the gas phase. The catalyst is typically in the liquid phase. Because the reactants are gaseous compounds, a high contact surface area between the gas and liquid phases is desirable to enhance good mass transfer. This high contact surface area between the catalyst solution and the gas phase can be provided in any suitable manner. In batch methods, the batch contents are thoroughly mixed during the reaction process. In continuous operation, the reactor feed gas can be contacted with the catalyst solution in, for example, a continuously flowing stirred autoclave, where the gas is preferably introduced through a perforated inlet (e.g., a sprayer) and dispersed at the bottom of the vessel. High contact between the catalyst and the gas feed can also be provided by dispersing a solution of Rh catalyst on a high-surface-area support, a technique well-known in the art as supported liquid-phase catalysis, or by providing Rh as part of a permeable gel.

[0180] The reaction can be carried out in batch mode or preferably on a continuous basis. One or more reactors can be used in continuous mode to carry out the reaction in one or more stages.

[0181] The H2 to CO ratio in the syngas used for hydroformylation is preferably in the range of 1.1:1 to 1.01:1, preferably 1.06:1 to 1.02:1. Typically, the syngas can be prepared in a manner that results in a hydrogen to CO ratio much higher than this, or otherwise initially provided. Excess hydrogen can be separated as needed and used in other reaction stages. For example, excess hydrogen can be used to reduce propionaldehyde to propanol. In some practical modes, the syngas used in the practice of this invention is anhydrous.

[0182] Conversion of propionaldehyde to downstream ethylene-derived chemicals

[0183] In one embodiment, step e) includes subjecting propionaldehyde to hydrogenation to produce n-propanol as a downstream ethylene-derived chemical.

[0184] Propanal can optionally react with hydrogen in a hydroformylation step or subsequently in a separate hydrogenation step to produce n-propanol. This hydrogenation is a well-known reaction and can be carried out by any suitable known method.

[0185] In one embodiment, hydrogenation is carried out in the liquid or gas phase with hydrogen in the presence of a hydrogenation catalyst. Homogeneous or heterogeneous catalysts can be used. Copper catalysts have proven to be most suitable. Typically, the reaction is carried out in the liquid phase over a fixed-bed catalyst at 20°C to 200°C and pressures up to 30 MPa. Hydrogenation in the gas phase is preferably carried out continuously. Further details can be found in Ullmann's Encyclopedia of Industrial Chemistry, 2018, Propanal Chapter, DOI:10.1002 / 14356007.a22_157. 3rd Edition.

[0186] In another embodiment, step e) comprises subjecting propionaldehyde to oxidation to produce propionic acid as a downstream ethylene-derived chemical. Oxidation can be carried out according to any known method. In this embodiment, oxidation is carried out using catalytic liquid-phase oxidation with atmospheric oxygen. The reaction is carried out at temperatures of 30°C–100°C and 1–3 bar using manganese(II) propionate as a catalyst and propionic acid as a solvent. Further details are given in Technische Organische Chemie - Grundstoffe, Zwischenprodukte, Finalprodukte, Polymere [Industrial Organic Chemistry - Basic Raw Materials, Intermediate Products, Final Products, Polymers]. 1st ed. Deutscher Verlag für Grundstoffindustrie [German Basic Industrial Publishing House], Leipzig 1992, p. 133.

[0187] In another embodiment, step e) includes converting propionaldehyde into trimethylolethane as a downstream ethylene-derived chemical. Trimethylolethane is produced by the condensation of propionaldehyde with excess formaldehyde (US 2790837; WO2012110436). Trimethylolethane is a multifunctional component used in polyester resins.

[0188] Environmental attribute data

[0189] Products manufactured according to the method of the present invention can be associated with one or more environmental attributes. An environmental attribute refers to any characteristic or feature related to the environmental impact of a chemical. Environmental attributes can indicate the environmental performance of starting materials or manufacturing processes. Environmental attributes can be related to the product's carbon footprint (PCF). Environmental attributes can also relate to, for example, the renewable, bio-based, and / or recycled content of input materials and / or chemical products.

[0190] The association of environmental attributes with the corresponding products follows specific rules and regulations. For example, biomass content and recycled content attributes can be handled according to relevant standards (e.g., ISCC PLUS or REDcert2). In principle, two so-called balance methods can be distinguished: material balance content and mass balance content. Material content, for example, specifies the actual bio-based carbon content in the product. It needs to be verifiable (e.g., through C14 analysis or using a bill of materials). How to determine biomass carbon content using a bill of materials is taught, for example, in DIN EN 16785-2.

[0191] Quality balance methodologies (such as those offered by ISCC PLUS or REDcert2) can be applied to both biomass and recycled content. The term "quality balance" refers to the process by which inputs and outputs, along with associated information, are transferred, monitored, and controlled as they flow through the relevant supply chain. Such a process is known as a chain of custody model. With the increasing focus on sustainable, renewable, or recycled feedstocks, it is becoming increasingly important for companies to be able to track and control the chains of custody in which they directly participate, and also to be able to communicate and credibly validate these chains of custody transparently. For example, a validated chain of custody can demonstrate the origin and sustainability of the feedstocks used, the different conversion and transport steps in the chain, and the efficiency of these steps.

[0192] The handling of environmental properties is highly complex and requires digital solutions. For example, the corresponding environmental properties associated with input materials (particularly the biomass content of bioethanol or the biomass or recycling content of pyrolysis oil, bionaphtha, or syngas) can be assigned to a balancing account, preferably numerical, associated with the corresponding environmental property. From such balancing accounts, they can be allocated to one or more products manufactured according to the present invention.

[0193] Any corresponding product manufactured according to the present invention can be further associated with a digital identifier. Such digital identifiers can be based on decentralized identifiers and / or blockchain technology. Digital identifiers are specifically designed to monitor and control environmental properties throughout the entire value chain, including subsequent recycling where applicable. These identifiers can persist (in digital form) as the corresponding chemical product associated with them is further processed. Typically, they facilitate the verification of the chain of custody.

[0194] The corresponding numerical methods designed to handle environmental properties are described in more detail in WO 2023 / 117903 A1, WO2023 / 117897, WO 2023 / 117950 A1, WO 2023 / 117972 A1 and WO 2023 / 112013 A1 (all of which are by BASF SE), all of which are incorporated herein by reference.

[0195] Chemical products manufactured according to the present invention can also be combined with one or more environmental properties and determined biocarbon content values ​​(e.g., measured via C14 or calculated via a bill of materials). The corresponding numerical methods are described in more detail in EP application 23171760.4, which is incorporated herein by reference.

Claims

1. A method for manufacturing one or more ethylene-derived chemicals having a bio-based carbon content, the method comprising the following steps: (a) Providing a first ethylene stream by (ai) providing a pyrolysis feed stream containing pyrolysis oil and fossil-based hydrocarbons, (a-ii) subjecting the pyrolysis feed stream to steam cracking to obtain pyrolysis effluent, (a-iii) recovering the first ethylene stream from the pyrolysis effluent; (b) providing a second ethylene stream having a bio-based carbon content by subjecting a feedstock containing bioethanol to dehydration; (c) combining the first ethylene stream and the second ethylene stream to obtain a combined ethylene stream; (d) converting the combined ethylene stream into at least one first-generation ethylene-derived chemical selected from (α) ethylene oxide, (β) ethylbenzene, (γ) dichloroethane; and (δ) propionaldehyde; and (e) optionally subjecting the first-generation ethylene-derived chemical to a chemical conversion or a series of chemical conversions to obtain downstream ethylene-derived chemicals.

2. The method according to claim 1, wherein, The first-generation ethylene-derived chemical is ethylene oxide, and the downstream ethylene-derived chemical is selected from ethylene glycol, polyethylene glycol, ethylene glycol ethers, and ethanolamine; the first-generation ethylene-derived chemical is ethylbenzene, and the downstream ethylene-derived chemical is styrene; the first-generation ethylene-derived chemical is dichloroethane, and the downstream ethylene-derived chemical is vinyl chloride. Alternatively, the first-generation ethylene-derived chemical is propionaldehyde, and the downstream ethylene-derived chemical is selected from propanol, propionic acid, and trimethylolpropane.

3. The method according to claim 2, wherein, The downstream ethylene-derived chemical is selected from ethanolamine, and step (e) further includes converting the ethanolamine into ethylamine; the downstream ethylene-derived chemical is styrene, and step (e) further includes converting the styrene into polystyrene; or the downstream ethylene-derived chemical is vinyl chloride, and step (e) further includes converting the vinyl chloride into polyvinyl chloride.

4. The method according to any one of the preceding claims, wherein, The pyrolyzer feed stream comprises, relative to the total weight of the pyrolyzer feed: Up to 40 wt.% of pyrolysis oil; and 60 to 99.9 wt.% of fossil-based hydrocarbons; preferably 1 to 35 wt.% of pyrolysis oil; and 65 to 99 wt.% of fossil-based hydrocarbons.

5. The method according to any one of the preceding claims, wherein, The pyrolysis oil is obtained by pyrolysis of waste containing at least one bio-based material with a carbon content greater than zero.

6. The method according to claim 5, wherein, The at least one material is selected from plastics and rubber.

7. The method according to any one of the preceding claims, wherein, The pyrolysis oil exhibits at least one of the following parameters: - a calorific value in the range of 35 to 46 kJ / g; and - a bromine value in the range of 2 to 160 g Br2 / 100g.

8. The method according to any one of the preceding claims, wherein, The pyrolyzer feed stream contains up to 10 wt.% of bio-naphtha relative to the total weight of the pyrolyzer feed stream.

9. The method according to claim 8, wherein, This bio-naphtha is obtained at least in part by the hydrogenation of fatty acids, fatty acid derivatives, monoglycerides, diglycerides or triglycerides, or combinations thereof.

10. The method according to any one of the preceding claims, wherein, The second ethylene stream has a bio-based carbon content in the range of 50% to 100%.

11. The method according to any one of the preceding claims, wherein, The downstream ethylene-derived chemicals have a carbon atom ratio from the merged ethylene stream to the total number of carbon atoms in the molecule that is ≥ 0.

25.

12. The method according to any one of the preceding claims, wherein, The weight ratio of the first ethylene stream to the second ethylene stream is selected such that the bio-based carbon content of the one or more ethylene-derived chemicals is at least 3%.

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